Heterocycle-substituted bicyclic azole pesticides

ABSTRACT

Disclosed are compounds of Formula 1, including all geometric and stereoisomers, N oxides, and salts thereof, wherein A, X 1 , X 2 , X 3  and R 2  are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or a composition of the invention.

FIELD OF THE INVENTION

This invention relates to certain substituted bicyclic azoles, theirN-oxides, salts and compositions suitable for agronomic and nonagronomicuses, and methods of their use for controlling invertebrate pests suchas arthropods in both agronomic and nonagronomic environments.

BACKGROUND OF THE INVENTION

The control of invertebrate pests is extremely important in achievinghigh crop efficiency. Damage by invertebrate pests to growing and storedagronomic crops can cause significant reduction in productivity andthereby result in increased costs to the consumer. The control ofinvertebrate pests in forestry, greenhouse crops, ornamentals, nurserycrops, stored food and fiber products, livestock, household, turf, woodproducts, and public and animal health is also important. Many productsare commercially available for these purposes, but the need continuesfor new compounds that are more effective, less costly, less toxic,environmentally safer or have different sites of action.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula 1 (including allgeometric and stereoisomers), N-oxides, and salts thereof, andcompositions containing them and their use for controlling invertebratepests:

wherein

-   -   A is CH, CF or N;    -   X¹ is CR¹, and X² is CR² or N; or X¹ is CR² or N, and X² is CR¹;    -   X³ is CR² or N;    -   R¹ is a 5- to 10-membered aromatic ring or ring system, each        ring or ring system containing ring members selected from carbon        atoms and up to 3 heteroatoms independently selected from one        oxygen atom, one sulfur atom, and up to 3 nitrogen atoms,        wherein up to 2 carbon atom ring members are independently        selected from C(═O) and C(═S) and the sulfur atom ring member is        selected from S, S(O) or S(O)₂, each ring or ring system being        substituted with one R³, and optionally further substituted with        1 to 3 R^(x); or    -   R¹ is a 3- to 6-membered partially saturated ring, each ring        containing ring members selected from carbon atoms and up to 2        heteroatoms independently selected from one oxygen atom, one        sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon        atom ring members are independently selected from C(═O) and        C(═S) and the sulfur atom ring member is selected from S, S(O)        or S(O)₂, each ring being substituted with one R³, and        optionally further substituted with at least one R^(x);    -   each R² is independently H, halogen, cyano, nitro, C₁-C₄ alkyl,        C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy;    -   R³ is selected from the group consisting of

-   -   each R⁴ is independently H or C₁-C₄ alkyl;    -   each R⁵ is independently H or C₁-C₄ alkyl; or    -   R⁴ and R⁵ are taken together with the carbon atom to which they        are attached to form a 3- to 6-membered ring containing ring        members selected from carbon atoms and up to 2 heteroatoms        independently selected from one oxygen atom, one sulfur atom,        and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring        members are independently selected from C(═O) and C(═S) and the        sulfur atom ring member is selected from S, S(O) or S(O)₂, said        ring being unsubstituted or substituted with up to 4 R^(x);        provided that R⁴ and R⁵ are attached to the same carbon atom;    -   p is 1, 2, 3 or 4;    -   R⁶ is H, NR¹³R¹⁴, OR¹⁵ or C(═NR⁸)R⁹; or C₁-C₆ alkyl substituted        with at least one R^(y); or C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or        C₂-C₆ alkynyl, each unsubstituted or substituted with at least        one R^(x);    -   R^(6a) is OC(═NR⁸)R⁹, OC(O)R⁹, NHC(═NR⁸)R⁹, NHC(O)R⁹,        SO₂NR¹³R¹⁴, SO₂OR¹⁵, SO₂C(═NR⁸)R⁹, C(═NR⁸)NR¹³R¹⁴, C(O)NR¹³R¹⁴,        C(═NR⁸)OR¹⁵ or C(O)OR¹⁵; or    -   R^(6a) is YR^(6b);    -   Y is O, S, NH or C(O);    -   R^(6b) is C₁-C₆ alkyl substituted with at least one R^(y); or        C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each        unsubstituted or substituted with at least one R^(x);    -   R⁷ is H, C(O)R¹⁷ or S(O)_(n)R¹⁸; or C₁-C₆ alkyl, C₃-C₆        cycloalkyl, C₃-C₆ cycloalkoxy, C₂-C₆ alkenyl or C₂-C₆ alkynyl,        each unsubstituted or substituted with at least one R^(x); or        phenyl or a 5- or 6-membered heterocyclic aromatic ring, or a 5-        or 6-membered heterocyclic non-aromatic ring, each unsubstituted        or substituted with at least one substituent independently        selected from the group consisting of halogen, cyano, nitro,        C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy,        C₃-C₆ cycloalkoxy and C₁-C₄ haloalkoxy;    -   provided that when R³ is R^(3b), R^(3d), R^(3e) or R^(3f), then        both R⁶ and R⁷ cannot be H;    -   each R^(x) is independently halogen, cyano, nitro, hydroxy,        C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₁-C₆ alkoxy,        C₁-C₆ haloalkoxy, C₃-C₆ cycloalkoxy, C(═NR⁸)R⁹, C(O)OR¹⁶,        C(O)NR¹³R¹⁴, OC(O)R¹⁷, NR²⁰R²¹, NR¹⁹C(O)R¹⁷, C(O)R¹⁷,        S(O)_(n)R¹⁸, Si(R²³)₃, OSi(R²³)₃ or Q;    -   each R^(y) is independently cyano, nitro, hydroxy, C₁-C₆ alkyl,        C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₁-C₆ alkoxy, C₁-C₆        haloalkoxy, C₃-C₆ cycloalkoxy, C(═NR⁸)R⁹, C(O)OR¹⁶, C(O)NR¹³R¹⁴,        OC(O)R¹⁷, NR²⁰R²¹, NR¹⁹C(O)R¹⁷, C(O)R¹⁷, S(O)_(n)R¹⁸, Si(R²³)₃,        OSi(R²³)₃ or Q;    -   each R⁸ is independently OR¹⁰, S(O)_(n)R¹¹ or NHR¹²;    -   each R⁹ is independently H; or C₁-C₆ alkyl, C₃-C₆ cycloalkyl,        C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted or        substituted with at least one R^(x); or C₁-C₆ alkoxy, C₁-C₆        haloalkoxy, C₃-C₆ cycloalkoxy, C(O)OR¹⁶, C(O)NR¹³R¹⁴, NR²⁰R²¹,        NR¹⁹C(O)R¹⁷, C(O)R¹⁷ or Q;    -   each R¹⁰ is independently C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C(O)R¹⁷, S(O)_(n)R¹¹ or Q;    -   each R¹¹ is independently C₁-C₄ alkyl or C₁-C₄ haloalkyl;    -   R¹² is C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C(O)R¹⁷        or C(O)OR¹⁶; or phenyl, unsubstituted or substituted with at        least one substituent independently selected from the group        consisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆        cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each R¹³ is independently H, C₁-C₆ alkyl, C₁-C₄ haloalkyl, C₁-C₄        hydroxyalkyl, C(O)R²² or S(O)₂R²²; or phenyl or a 5- or        6-membered heterocyclic aromatic ring, each unsubstituted or        substituted with at least one substituent independently selected        from the group consisting of halogen, cyano, nitro, C₁-C₄ alkyl,        C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄        haloalkoxy;    -   each R¹⁴ is independently H, C₁-C₆ alkyl or C₁-C₄ haloalkyl; or    -   R¹³ and R¹⁴ are taken together with the nitrogen atom to which        they are attached to form a 3- to 7-membered ring containing        ring members selected from carbon atoms and up to 2 heteroatoms        independently selected from one oxygen atom, one sulfur atom,        and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring        members are independently selected from C(═O) and C(═S) and the        sulfur atom ring member is selected from S, S(O) or S(O)₂, said        ring being unsubstituted or substituted with at least one        substituent independently selected from the group consisting of        halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   R¹⁵ is C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₃-C₆ cycloalkoxy or C₁-C₄        haloalkyl; or phenyl, unsubstituted or substituted with at least        one substituent independently selected from the group consisting        of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each R¹⁶ is independently H, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₃-C₆        cycloalkyl or C₃-C₆ halocycloalkyl; or phenyl, unsubstituted or        substituted with at least one substituent independently selected        from the group consisting of halogen, cyano, nitro, C₁-C₄ alkyl,        C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄        haloalkoxy;    -   each R¹⁷ is independently C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₃-C₆        cycloalkyl or C₃-C₆ halocycloalkyl; or phenyl, unsubstituted or        substituted with at least one substituent independently selected        from the group consisting of halogen, cyano, nitro, C₁-C₄ alkyl,        C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄        haloalkoxy;    -   each R¹⁸ is independently C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₃-C₆        cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ cycloalkylalkyl or C₃-C₆        halocycloalkylalkyl; or phenyl, unsubstituted or substituted        with at least one substituent independently selected from the        group consisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆        cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each R¹⁹ is independently H or C₁-C₄ alkyl;    -   each R²⁰ is independently H, C₁-C₄ alkyl or C₁-C₄ haloalkyl; or        phenyl, unsubstituted or substituted with at least one        substituent independently selected from the group consisting of        halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each R²¹ is independently H, C₁-C₄ alkyl or C₁-C₄ haloalkyl; or        phenyl, unsubstituted or substituted with at least one        substituent independently selected from the group consisting of        halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; or    -   R²⁰ and R²¹ are independently taken together with the nitrogen        atom to which they are attached to form a 3- to 7-membered ring        containing ring members selected from carbon atoms and up to 2        heteroatoms independently selected from one oxygen atom, one        sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon        atom ring members are independently selected from C(═O) and        C(═S) and the sulfur atom ring member is selected from S, S(O)        or S(O)₂, said ring being unsubstituted or substituted with at        least one substituent independently selected from the group        consisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆        cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each R²² is independently C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆        alkoxy, C₁-C₆ haloalkoxy or NR²⁴R²⁵; or phenyl or a 5- or        6-membered heterocyclic aromatic ring, each unsubstituted or        substituted with at least one substituent independently selected        from the group consisting of halogen, cyano, nitro, C₁-C₄ alkyl,        C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄        haloalkoxy;    -   each R²³ is independently C₁-C₆ alkyl, C₃-C₆ cycloalkyl or        phenyl;    -   each R²⁴ is independently H or Q; or C₁-C₆ alkyl, C₃-C₆        cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted        or substituted with at least one substituent independently        selected from the group consisting of halogen, cyano, nitro,        C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and        C₁-C₄ haloalkoxy;    -   each R²⁵ is independently H or Q; or C₁-C₆ alkyl, C₃-C₆        cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted        or substituted with at least one substituent independently        selected from the group consisting of halogen, cyano, nitro,        C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and        C₁-C₄ haloalkoxy; or    -   R²⁴ and R²⁵ are taken together with the nitrogen atom to which        they are attached to form a 3- to 10-membered ring containing        ring members selected from carbon atoms and up to 2 heteroatoms        independently selected from one oxygen atom, one sulfur atom,        and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring        members are independently selected from C(═O) and C(═S) and the        sulfur atom ring member is selected from S, S(O) or S(O)₂, said        ring being unsubstituted or substituted with up to 4        substituents independently selected from the group consisting of        halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each Q is independently phenyl, a 5- or 6-membered heterocyclic        aromatic ring or a 3- to 6-membered heterocyclic non-aromatic        ring, each ring containing ring members selected from carbon        atoms and up to 2 heteroatoms independently selected from one        oxygen atom, one sulfur atom, and up to 2 nitrogen atoms,        wherein up to 2 carbon atom ring members are independently        selected from C(═O) and C(═S) and the sulfur atom ring member is        selected from S, S(O) or S(O)₂, each ring unsubstituted or        substituted with at least one substituent independently selected        from the group consisting of halogen, cyano, nitro, C₁-C₄ alkyl,        C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄        haloalkoxy; and    -   each n is independently 0, 1 or 2.

This invention also provides a composition comprising a compound ofFormula 1, an N-oxide or a salt thereof, and at least one additionalcomponent selected from the group consisting of surfactants, soliddiluents and liquid diluents. In one embodiment, this invention alsoprovides a composition for controlling an invertebrate pest comprising acompound of Formula 1, an N-oxide or a salt thereof, and at least oneadditional component selected from the group consisting of surfactants,solid diluents and liquid diluents, said composition optionally furthercomprising at least one additional biologically active compound oragent.

This invention provides a method for controlling an invertebrate pestcomprising contacting the invertebrate pest or its environment with abiologically effective amount of a compound of Formula 1, an N-oxide ora salt thereof, (e.g., as a composition described herein). Thisinvention also relates to such method wherein the invertebrate pest orits environment is contacted with a composition comprising abiologically effective amount of a compound of Formula 1, an N-oxide ora salt thereof, and at least one additional component selected from thegroup consisting of surfactants, solid diluents and liquid diluents,said composition optionally further comprising a biologically effectiveamount of at least one additional biologically active compound or agent.

This invention also provides a method for protecting a seed from aninvertebrate pest comprising contacting the seed with a biologicallyeffective amount of a compound of Formula 1, an N-oxide or a saltthereof, (e.g., as a composition described herein). This invention alsorelates to the treated seed. This invention further provides a methodfor protecting an animal from an invertebrate parasitic pest comprisingadministering to the animal a parasiticidally effective amount of acompound of Formula 1, an N-oxide or a salt thereof, (e.g., as acomposition described herein). This invention also provides for the useof a compound of Formula 1, an N-oxide or a salt thereof, (e.g., as acomposition described herein) in protecting an animal from aninvertebrate pest.

This invention also provides a method for increasing vigor of a cropplant comprising contacting the crop plant, the seed from which the cropplant is grown or the locus (e.g., growth medium) of the crop plant witha biologically effective amount of a compound of Formula 1 (e.g., as acomposition described herein).

DETAILS OF THE INVENTION

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” “contains”, “containing,” “characterizedby” or any other variation thereof, are intended to cover anon-exclusive inclusion, subject to any limitation explicitly indicated.For example, a composition, mixture, process or method that comprises alist of elements is not necessarily limited to only those elements butmay include other elements not expressly listed or inherent to suchcomposition, mixture, process or method.

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim, such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistingof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition or method that includes materials, steps, features,components, or elements, in addition to those literally disclosed,provided that these additional materials, steps, features, components,or elements do not materially affect the basic and novelcharacteristic(s) of the claimed invention. The term “consistingessentially of” occupies a middle ground between “comprising” and“consisting of”.

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso describe such an invention using the terms “consisting essentiallyof” or “consisting of.”

Further, unless expressly stated to the contrary, “or” refers to aninclusive or and not to an exclusive or. For example, a condition A or Bis satisfied by any one of the following: A is true (or present) and Bis false (or not present), A is false (or not present) and B is true (orpresent), and both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element orcomponent of the invention are intended to be nonrestrictive regardingthe number of instances (i.e. occurrences) of the element or component.Therefore “a” or “an” should be read to include one or at least one, andthe singular word form of the element or component also includes theplural unless the number is obviously meant to be singular.

As referred to in this disclosure, the term “invertebrate pest” includesarthropods, gastropods, nematodes and helminths of economic importanceas pests. The term “arthropod” includes insects, mites, spiders,scorpions, centipedes, millipedes, pill bugs and symphylans. The term“gastropod” includes snails, slugs and other Stylommatophora. The term“nematode” includes members of the phylum Nematoda, such as phytophagousnematodes and helminth nematodes parasitizing animals. The term“helminth” includes all of the parasitic worms, such as roundworms(phylum Nematoda), heartworms (phylum Nematoda, class Secernentea),flukes (phylum Platyhelminthes, class Tematoda), acanthocephalans(phylum Acanthocephala), and tapeworms (phylum Platyhelminthes, classCestoda).

In the context of this disclosure “invertebrate pest control” meansinhibition of invertebrate pest development (including mortality,feeding reduction, and/or mating disruption), and related expressionsare defined analogously.

The term “agronomic” refers to the production of field crops such as forfood and fiber and includes the growth of maize or corn, soybeans andother legumes, rice, cereal (e.g., wheat, oats, barley, rye and rice),leafy vegetables (e.g., lettuce, cabbage, and other cole crops),fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers andcucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g.,pome, stone and citrus), small fruit (e.g., berries and cherries) andother specialty crops (e.g., canola, sunflower and olives).

The term “nonagronomic” refers to other than field crops, such ashorticultural crops (e.g., greenhouse, nursery or ornamental plants notgrown in a field), residential, agricultural, commercial and industrialstructures, turf (e.g., sod farm, pasture, golf course, lawn, sportsfield, etc.), wood products, stored product, agro-forestry andvegetation management, public health (i.e. human) and animal health(e.g., domesticated animals such as pets, livestock and poultry,undomesticated animals such as wildlife) applications.

The term “crop vigor” refers to rate of growth or biomass accumulationof a crop plant. An “increase in vigor” refers to an increase in growthor biomass accumulation in a crop plant relative to an untreated controlcrop plant. The term “crop yield” refers to the return on crop material,in terms of both quantity and quality, obtained after harvesting a cropplant. An “increase in crop yield” refers to an increase in crop yieldrelative to an untreated control crop plant.

The term “biologically effective amount” refers to the amount of abiologically active compound (e.g., a compound of Formula 1) sufficientto produce the desired biological effect when applied to (i.e. contactedwith) an invertebrate pest to be controlled or its environment, or to aplant, the seed from which the plant is grown, or the locus of the plant(e.g., growth medium) to protect the plant from injury by theinvertebrate pest or for other desired effect (e.g., increasing plantvigor).

A wavy line in a structure fragment (for example, R^(3a) through R^(3f))denotes the attachment point of the fragment to the remainder of themolecule.

In the above recitations, the term “alkyl”, used either alone or incompound words such as “alkylthio” or “haloalkyl” includesstraight-chain or branched alkyl, such as, methyl, ethyl, n-propyl,i-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl”includes straight-chain or branched alkenes such as ethenyl, 1-propenyl,2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.“Alkenyl” also includes polyenes such as 1,2-propadienyl and2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynessuch as ethynyl, 1-propynyl, 2-propynyl and the different butynyl,pentynyl and hexynyl isomers. “Alkynyl” can also include moietiescomprised of multiple triple bonds such as 2,5-hexadiynyl.

“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy,isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.“Alkylthio” includes branched or straight-chain alkylthio moieties suchas methylthio, ethylthio, and the different propylthio, butylthio,pentylthio and hexylthio isomers.

“Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyland cyclohexyl.

The term “halogen”, either alone or in compound words such as“haloalkyl”, or when used in descriptions such as “alkyl substitutedwith halogen” includes fluorine, chlorine, bromine or iodine. Further,when used in compound words such as “haloalkyl”, or when used indescriptions such as “alkyl substituted with halogen” said alkyl may bepartially or fully substituted with halogen atoms which may be the sameor different. Examples of “haloalkyl” or “alkyl substituted withhalogen” include F₃C—, ClCH₂—, CF₃CH₂— and CF₃CCl₂—. The terms“halocycloalkyl”, “haloalkoxy”, “haloalkylthio”, “haloalkenyl”,“haloalkynyl”, and the like, are defined analogously to the term“haloalkyl”. Examples of “haloalkoxy” include CF₃O—, CCl₃CH₂O—,HCF₂CH₂CH₂O— and CF₃CH₂O—. Examples of “haloalkylthio” include CCl₃S—,CF₃S—, CCl₃CH₂S— and ClCH₂CH₂CH₂S—.

The chemical abbreviations S(O) and S(═O) as used herein represent asulfinyl moiety. The chemical abbreviations SO₂, S(O)₂ and S(═O)₂ asused herein represent a sulfonyl moiety. The chemical abbreviations C(O)and C(═O) as used herein represent a carbonyl moiety. The chemicalabbreviations CO₂, C(O)O and C(═O)O as used herein represent anoxycarbonyl moiety. “CHO” means formyl.

The total number of carbon atoms in a substituent group is indicated bythe “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 6. Forexample, C₁-C₄ alkylsulfonyl designates methylsulfonyl throughbutylsulfonyl; C₂ alkoxyalkyl designates CH₃OCH₂—; C₃ alkoxyalkyldesignates, for example, CH₃CH(OCH₃)—, CH₃OCH₂CH₂— or CH₃CH₂OCH₂—; andC₄ alkoxyalkyl designates the various isomers of an alkyl groupsubstituted with an alkoxy group containing a total of four carbonatoms, examples including CH₃CH₂CH₂OCH₂— and CH₃CH₂OCH₂CH₂—.

When a compound is substituted with a substituent bearing a subscriptthat indicates the number of said substituents can exceed 1, saidsubstituents (when they exceed 1) are independently selected from thegroup of defined substituents. Further, when the subscript indicates arange, e.g. (R)_(i-j), then the number of substituents may be selectedfrom the integers between i and j inclusive. When a group contains asubstituent which can be hydrogen, then when this substituent is takenas hydrogen, it is recognized that this is equivalent to said groupbeing unsubstituted. When one or more positions on a group are said tobe “not substituted” or “unsubstituted”, then hydrogen atoms areattached to take up any free valency.

Unless otherwise indicated, a “ring” or “ring system” as a component ofFormula 1 (e.g., substituent Q^(a)) is carbocyclic or heterocyclic. Theterm “ring system” denotes two or more fused rings. The terms “bicyclicring system” and “fused bicyclic ring system” denote a ring systemconsisting of two fused rings, which can be “ortho-fused”, “bridgedbicyclic” or “spirobicyclic”. An “ortho-fused bicyclic ring system”denotes a ring system wherein the two constituent rings have twoadjacent atoms in common. A “bridged bicyclic ring system” is formed bybonding a segment of one or more atoms to nonadjacent ring members of aring. A “spirobicyclic ring system” is formed by bonding a segment oftwo or more atoms to the same ring member of a ring. The term “fusedheterobicyclic ring system” denotes a fused bicyclic ring system inwhich at least one ring atom is not carbon. The term “ring member”refers to an atom or other moiety (e.g., C(═O), C(═S), S(O) or S(O)₂)forming the backbone of a ring or ring system.

The terms “carbocyclic ring”, “carbocycle” or “carbocyclic ring system”denote a ring or ring system wherein the atoms forming the ring backboneare selected only from carbon. The terms “heterocyclic ring”,“heterocycle” or “heterocyclic ring system” denote a ring or ring systemin which at least one atom forming the ring backbone is not carbon,e.g., nitrogen, oxygen or sulfur. Typically a heterocyclic ring containsno more than 4 nitrogens, no more than 2 oxygens and no more than 2sulfurs. Unless otherwise indicated, a carbocyclic ring or heterocyclicring can be a saturated or unsaturated ring. “Saturated” refers to aring having a backbone consisting of atoms linked to one another bysingle bonds; unless otherwise specified, the remaining atom valencesare occupied by hydrogen atoms. Unless otherwise stated, an “unsaturatedring” may be partially unsaturated or fully unsaturated. The expression“fully unsaturated ring” means a ring of atoms in which the bondsbetween atoms in the ring are single or double bonds according tovalence bond theory and furthermore the bonds between atoms in the ringinclude as many double bonds as possible without double bonds beingcumulative (i.e. no C═C═C or C═C═N). The term “partially unsaturatedring” denotes a ring comprising at least one ring member bonded to anadjacent ring member through a double bond and which conceptuallypotentially accommodates a number of non-cumulated double bonds betweenadjacent ring members (i.e. in its fully unsaturated counterpart form)greater than the number of double bonds present (i.e. in its partiallyunsaturated form).

Unless otherwise indicated, heterocyclic rings and ring systems can beattached through any available carbon or nitrogen by replacement of ahydrogen on said carbon or nitrogen.

“Aromatic” indicates that each of the ring atoms is essentially in thesame plane and has a p-orbital perpendicular to the ring plane, and inwhich (4n+2) it electrons, where n is a positive integer, are associatedwith the ring to comply with Hückel's rule. The term “aromatic ringsystem” denotes a carbocyclic or heterocyclic ring system in which atleast one ring of the ring system is aromatic. When a fully unsaturatedcarbocyclic ring satisfies Hückel's rule, then said ring is also calledan “aromatic ring” or “aromatic carbocyclic ring”. The term “aromaticcarbocyclic ring system” denotes a carbocyclic ring system in which atleast one ring of the ring system is aromatic. When a fully unsaturatedheterocyclic ring satisfies Hückel's rule, then said ring is also calleda “heteroaromatic ring”, “aromatic heterocyclic ring” or “heterocyclicaromatic ring”. The term “aromatic heterocyclic ring system” denotes aheterocyclic ring system in which at least one ring of the ring systemis aromatic. The term “nonaromatic ring system” denotes a carbocyclic orheterocyclic ring system that may be fully saturated, as well aspartially or fully unsaturated, provided that none of the rings in thering system are aromatic. The term “nonaromatic carbocyclic ring system”denotes a carbocyclic ring in which no ring in the ring system isaromatic. The term “nonaromatic heterocyclic ring system” denotes aheterocyclic ring system in which no ring in the ring system isaromatic.

The term “optionally substituted” in connection with the heterocyclicrings refers to groups which are unsubstituted or have at least onenon-hydrogen substituent that does not extinguish the biologicalactivity possessed by the unsubstituted analog. As used herein, thefollowing definitions shall apply unless otherwise indicated. The term“optionally substituted” is used interchangeably with the phrase“substituted or unsubstituted” or with the term “(un)substituted.”Unless otherwise indicated, an optionally substituted group may have asubstituent at each substitutable position of the group, and eachsubstitution is independent of the other.

When a substituent is a 5- or 6-membered nitrogen-containingheterocyclic ring, it may be attached to the remainder of Formula 1though any available carbon or nitrogen ring atom, unless otherwisedescribed. As noted above, Q can be (among others) phenyl optionallysubstituted with one or more substituents selected from a group ofsubstituents as defined in the Summary of Invention. An example ofphenyl optionally substituted with one to five substituents is the ringillustrated as U-1 in Exhibit 1, wherein R^(v) is R^(x) as defined inthe Summary of the Invention for Q and r is an integer from 0 to 5.

As noted above, Q can be (among others) a 5- or 6-membered heterocyclicaromatic ring, optionally substituted with one or more substituentsselected from a group of substituents as defined in the Summary ofInvention. Examples of a 5- or 6-membered unsaturated aromaticheterocyclic ring optionally substituted with from one or moresubstituents include the rings U-2 through U-61 illustrated in Exhibit 1wherein R^(v) is any substituent as defined in the Summary of theInvention for Q and r is an integer from 0 to 4, limited by the numberof available positions on each U group. As U-29, U-30, U-36, U-37, U-38,U-39, U-40, U-41, U-42 and U-43 have only one available position, forthese U groups r is limited to the integers 0 or 1, and r being 0 meansthat the U group is unsubstituted and a hydrogen is present at theposition indicated by (R^(v))_(r).

Although R^(v) groups are shown in the structures U-1 through U-61, itis noted that they do not need to be present since they are optionalsubstituents. Note that when R^(v) is H when attached to an atom, thisis the same as if said atom is unsubstituted. The nitrogen atoms thatrequire substitution to fill their valence are substituted with H orR^(v). Note that when the attachment point between (R^(v))_(r) and the Ugroup is illustrated as floating, (R^(v))_(r) can be attached to anyavailable carbon atom or nitrogen atom of the U group. Note that whenthe attachment point on the U group is illustrated as floating, the Ugroup can be attached to the remainder of Formula 1 through anyavailable carbon or nitrogen of the U group by replacement of a hydrogenatom. Note that some U groups can only be substituted with less than 4R^(v) groups (e.g., U-2 through U-5, U-7 through U-48, and U-52 throughU-61).

A wide variety of synthetic methods are known in the art to enablepreparation of aromatic and nonaromatic heterocyclic rings and ringsystems; for extensive reviews see the eight volume set of ComprehensiveHeterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief,Pergamon Press, Oxford, 1984 and the twelve volume set of ComprehensiveHeterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V.Scriven editors-in-chief, Pergamon Press, Oxford, 1996.

Compounds of this invention can exist as one or more stereoisomers.Stereoisomers are isomers of identical constitution but differing in thearrangement of their atoms in space and include enantiomers,diastereomers, cis-trans isomers (also known as geometric isomers) andatropisomers. Atropisomers result from restricted rotation about singlebonds where the rotational barrier is high enough to permit isolation ofthe isomeric species. One skilled in the art will appreciate that onestereoisomer may be more active and/or may exhibit beneficial effectswhen enriched relative to the other stereoisomer(s) or when separatedfrom the other stereoisomer(s). Additionally, the skilled artisan knowshow to separate, enrich, and/or to selectively prepare saidstereoisomers. For a comprehensive discussion of all aspects ofstereoisomerism, see Ernest L. Eliel and Samuel H. Wilen,Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

This invention comprises all stereoisomers, conformational isomers andmixtures thereof in all proportions as well as isotopic forms such asdeuterated compounds.

One skilled in the art will appreciate that not all nitrogen-containingheterocycles can form N-oxides since the nitrogen requires an availablelone pair for oxidation to the oxide; one skilled in the art willrecognize those nitrogen-containing heterocycles which can formN-oxides. One skilled in the art will also recognize that tertiaryamines can form N-oxides. Synthetic methods for the preparation ofN-oxides of heterocycles and tertiary amines are very well known by oneskilled in the art including the oxidation of heterocycles and tertiaryamines with peroxy acids such as peracetic and 3-chloroperbenzoic acid(MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butylhydroperoxide, sodium perborate, and dioxiranes such asdimethyldioxirane. These methods for the preparation of N-oxides havebeen extensively described and reviewed in the literature, see forexample: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik inComprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boultonand A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keenein Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R.Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advancesin Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J.Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G.Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A.R. Katritzky and A. J. Boulton, Eds., Academic Press.

One skilled in the art recognizes that because in the environment andunder physiological conditions salts of chemical compounds are inequilibrium with their corresponding nonsalt forms, salts share thebiological utility of the nonsalt forms. Thus a wide variety of salts ofthe compounds of Formula 1 are useful for control of invertebrate pests.The salts of the compounds of Formula 1 include acid-addition salts withinorganic or organic acids such as hydrobromic, hydrochloric, nitric,phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic,oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valericacids. When a compound of Formula 1 contains an acidic moiety such as acarboxylic acid or phenol, salts also include those formed with organicor inorganic bases such as pyridine, triethylamine or ammonia, oramides, hydrides, hydroxides or carbonates of sodium, potassium,lithium, calcium, magnesium or barium. Accordingly, the presentinvention comprises compounds selected from Formula 1, N-oxides andsuitable salts thereof.

Compounds selected from Formula 1, stereoisomers, tautomers, N-oxides,and salts thereof, typically exist in more than one form, and Formula 1thus includes all crystalline and non-crystalline forms of the compoundsthat Formula 1 represents. Non-crystalline forms include embodimentswhich are solids such as waxes and gums as well as embodiments which areliquids such as solutions and melts. Crystalline forms includeembodiments which represent essentially a single crystal type andembodiments which represent a mixture of polymorphs (i.e. differentcrystalline types). The term “polymorph” refers to a particularcrystalline form of a chemical compound that can crystallize indifferent crystalline forms, these forms having different arrangementsand/or conformations of the molecules in the crystal lattice. Althoughpolymorphs can have the same chemical composition, they can also differin composition due to the presence or absence of co-crystallized wateror other molecules, which can be weakly or strongly bound in thelattice. Polymorphs can differ in such chemical, physical and biologicalproperties as crystal shape, density, hardness, color, chemicalstability, melting point, hygroscopicity, suspensibility, dissolutionrate and biological availability. One skilled in the art will appreciatethat a polymorph of a compound represented by Formula 1 can exhibitbeneficial effects (e.g., suitability for preparation of usefulformulations, improved biological performance) relative to anotherpolymorph or a mixture of polymorphs of the same compound represented byFormula 1. Preparation and isolation of a particular polymorph of acompound represented by Formula 1 can be achieved by methods known tothose skilled in the art including, for example, crystallization usingselected solvents and temperatures. Compounds of this invention mayexist as one or more crystalline polymorphs. This invention comprisesboth individual polymorphs and mixtures of polymorphs, includingmixtures enriched in one polymorph relative to others. For acomprehensive discussion of polymorphism see R. Hilfiker, Ed.,Polymorphism In the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.

Embodiments of the present invention as described in the Summary of theInvention include those described below. In the following Embodiments,reference to “a compound of Formula 1” includes the definitions ofsubstituents specified in the Summary of the Invention unless furtherdefined in the Embodiments.

-   -   Embodiment 1. A compound of Formula 1 wherein A is CH, CF or N.    -   Embodiment 1a. A compound of Formula 1 wherein A is CH or CF.    -   Embodiment 1b. A compound of Formula 1 wherein A is CF or N.    -   Embodiment 1c. A compound of Formula 1 wherein A is CH.    -   Embodiment 1d. A compound of Formula 1 wherein A is CF.    -   Embodiment 1e. A compound of Formula 1 wherein A is N.    -   Embodiment 2. A compound of Formula 1 wherein X¹ is CR¹.    -   Embodiment 2a. A compound of Formula 1 wherein X¹ is CR¹ and X²        is CR² or N.    -   Embodiment 2b. A compound of Formula 1 wherein X¹ is CR¹ and X²        is CR².    -   Embodiment 2c. A compound of Formula 1 wherein X¹ is CR¹ and X²        is CH or CF.    -   Embodiment 2d. A compound of Formula 1 wherein X¹ is CR¹ and X²        is CH or N.    -   Embodiment 2e. A compound of Formula 1 wherein X¹ is CR¹ and X²        is CH.    -   Embodiment 2f. A compound of Formula 1 wherein X¹ is CR¹ and X²        is N.    -   Embodiment 2g. A compound of Formula 1 wherein X¹ is CR¹, X² is        CH, and X³ is CH or CF.    -   Embodiment 2h. A compound of Formula 1 wherein X¹ is CR¹, X² is        CH, and X³ is N.    -   Embodiment 3. A compound of Formula 1 wherein X² is CR¹.    -   Embodiment 3a. A compound of Formula 1 wherein X² is CR¹ and X¹        is CR² or N.    -   Embodiment 3b. A compound of Formula 1 wherein X² is CR¹ and X¹        is CR².    -   Embodiment 3c. A compound of Formula 1 wherein X² is CR¹ and X¹        is CH or CF.    -   Embodiment 3d. A compound of Formula 1 wherein X² is CR¹ and X¹        is CH or N.    -   Embodiment 3e. A compound of Formula 1 wherein X² is CR¹ and X¹        is CH.    -   Embodiment 3f. A compound of Formula 1 wherein X² is CR¹ and X¹        is N.    -   Embodiment 3g. A compound of Formula 1 wherein X² is CR¹, X¹ is        CH, and X³ is CH or CF.    -   Embodiment 3h. A compound of Formula 1 wherein X² is CR¹, X¹ is        CH, and X³ is N.    -   Embodiment 4. A compound of Formula 1 wherein X¹ is CR¹ and X²        is CH or N; or X¹ is CH or N, and X² is CR¹.    -   Embodiment 4a. A compound of Formula 1 wherein X¹ is CR¹ and X²        is CH; or X¹ is CH, and X² is CR¹.    -   Embodiment 5. A compound of Formula 1 wherein X³ is N.    -   Embodiment 6. A compound of Formula 1 or any of Embodiments 1-5        wherein R¹ is a 5- to 10-membered aromatic ring or ring system,        each ring or ring system containing ring members selected from        carbon atoms and up to 3 heteroatoms independently selected from        one oxygen atom, one sulfur atom, and up to 3 nitrogen atoms,        wherein up to 2 carbon atom ring members are independently        selected from C(═O) and C(═S) and the sulfur atom ring member is        selected from S, S(O) or S(O)₂, each ring or ring system being        substituted with one R³, and optionally further substituted with        1 to 3 R^(x).    -   Embodiment 6a. A compound of Formula 1 or any of Embodiments 1-5        wherein R¹ is a 5- or 6-membered aromatic ring containing ring        members selected from carbon atoms and up to 3 heteroatoms        independently selected from one oxygen atom, one sulfur atom,        and up to 3 nitrogen atoms, wherein up to 2 carbon atom ring        members are independently selected from C(═O) and C(═S) and the        sulfur atom ring member is selected from S, S(O) or S(O)₂, each        ring being substituted with one R³, and optionally further        substituted with 1 to 3 R^(x).    -   Embodiment 6b. A compound of Formula 1 or any of Embodiments 1-5        wherein R¹ is phenyl, pyridinyl, thiazolyl, oxazolyl or        thiadiazolyl, each ring being substituted with one R³, and        optionally further substituted with 1 to 3 R^(x).    -   Embodiment 6c. A compound of Formula 1 or any of Embodiments 1-5        wherein R¹ is phenyl, 4-pyridinyl, 2-thiazolyl, 2-oxazolyl or        2-oxadiazolyl, each ring being substituted with one R³, and        optionally further substituted with 1 to 3 R^(x).    -   Embodiment 6d. A compound of Formula 1 or any of Embodiments 1-5        wherein R¹ is phenyl substituted with one R³, and optionally        further substituted with 1 to 3 R^(x).    -   Embodiment 6e. A compound of Formula 1 or any of Embodiments 1-5        wherein R¹ is 4-pyridinyl substituted with one R³, and        optionally further substituted with 1 to 3 R^(x).    -   Embodiment 6f. A compound of Formula 1 or any of Embodiments 1-5        wherein R¹ is 2-thiazolyl substituted with one R³, and        optionally further substituted with 1 R^(x).    -   Embodiment 6g. A compound of Formula 1 or any of Embodiments 1-5        wherein R¹ is 2-oxazolyl substituted with one R³, and optionally        further substituted with 1 R^(x).    -   Embodiment 6h. A compound of Formula 1 or any of Embodiments 1-5        wherein R¹ is 2-oxadiazolyl substituted with one R³.    -   Embodiment 7. A compound of Formula 1 or any of Embodiments 1-6h        wherein each R² is independently H or F.    -   Embodiment 7a. A compound of Formula 1 or any of Embodiments        1-6h wherein R² is H.    -   Embodiment 8. A compound of Formula 1 or any of Embodiments 1-7a        wherein R³ is R^(3b) or R^(3c).    -   Embodiment 8a. A compound of Formula 1 or any of Embodiments        1-7a wherein R³ is R^(3b).    -   Embodiment 8b. A compound of Formula 1 or any of Embodiments        1-7a wherein R³ is R^(3c).    -   Embodiment 8c. A compound of Formula 1 or any of Embodiments        1-7a wherein R³ is R^(3c), R^(6a) is YR^(6b), and Y is O.    -   Embodiment 8d. A compound of Formula 1 or any of Embodiments        1-7a wherein R³ is R^(3b) or R^(3e).    -   Embodiment 8e. A compound of Formula 1 or any of Embodiments        1-7a wherein R³ is R^(3e).    -   Embodiment 9. A compound of Formula 1 or any of Embodiments 1-8e        wherein R⁴ and R⁵ are each H, or are each methyl, or are taken        together with the carbon atom to which they are attached to form        a cyclopropane ring.    -   Embodiment 9a. A compound of Formula 1 or any of Embodiments        1-8e wherein R⁴ and R⁵ are each H, or are each methyl.    -   Embodiment 9b. A compound of Formula 1 or any of Embodiments        1-8e wherein R⁴ and R⁵ are each H.    -   Embodiment 9c. A compound of Formula 1 or any of Embodiments        1-8e wherein R⁴ and R⁵ are each methyl.    -   Embodiment 9d. A compound of Formula 1 or any of Embodiments        1-8e wherein R⁴ and R⁵ are taken together with the carbon atom        to which they are attached to form a cyclopropane ring.

Embodiments of this invention, including Embodiments 1-9d above as wellas any other embodiments described herein, can be combined in anymanner, and the descriptions of variables in the embodiments pertain notonly to the compounds of Formula 1 but also to the starting compoundsand intermediate compounds useful for preparing the compounds ofFormula 1. In addition, embodiments of this invention, includingEmbodiments 1-9d above as well as any other embodiments describedherein, and any combination thereof, pertain to the compositions andmethods of the present invention.

Combinations of Embodiments 1-9d are illustrated by:

-   -   Embodiment A. A compound of Formula 1 wherein    -   X¹ is CR¹ and X² is CH or N; or X¹ is CH or N, and X² is CR¹.    -   Embodiment B. A compound of Embodiment A wherein    -   R³ is R^(3b) or R^(3c).    -   Embodiment C. A compound of Embodiment B wherein    -   each R² is independently H or F.    -   Embodiment D. A compound of Embodiment C wherein    -   R¹ is phenyl, pyridinyl, thiazolyl, oxazolyl or thiadizolyl,        each being substituted with one R³, and optionally further        substituted with 1 to 3 R^(x).    -   Embodiment E. A compound of Formula 1 wherein    -   X¹ is CR¹ and X² is CR²; or X¹ is CR² and X² is CR¹;    -   R¹ is a 5- to 10-membered aromatic ring or ring system, each        ring or ring system containing ring members selected from carbon        atoms and up to 3 heteroatoms independently selected from one        oxygen atom, one sulfur atom, and up to 3 nitrogen atoms,        wherein up to 2 carbon atom ring members are independently        selected from C(═O) and C(═S) and the sulfur atom ring member is        selected from S, S(O) or S(O)₂, each ring or ring system being        substituted with one R³, and optionally further substituted with        1 to 3 R^(x).    -   each R² is independently H or F; and    -   R³ is R^(3b) or R^(3c).    -   Embodiment F. A compound of Formula 1 wherein    -   X¹ is CR¹ and X² is CR²; or X¹ is CR² and X² is CR¹;    -   R¹ is phenyl, pyridinyl, thiazolyl, oxazolyl or thiadizolyl,        each being substituted with one R³, and optionally further        substituted with 1 to 3 R^(x);    -   each R² is independently H or F; and    -   R³ is R^(3b) or R^(3c).    -   Embodiment G. A compound of Embodiment A wherein    -   X¹ is CR¹ and X² is CH; or X¹ is CH, and X² is CR¹.    -   Embodiment H. A compound of Embodiment G wherein    -   R¹ is a 5- or 6-membered aromatic ring containing ring members        selected from carbon atoms and up to 3 heteroatoms independently        selected from one oxygen atom, one sulfur atom, and up to 3        nitrogen atoms, wherein up to 2 carbon atom ring members are        independently selected from C(═O) and C(═S) and the sulfur atom        ring member is selected from S, S(O) or S(O)₂, each ring being        substituted with one R³, and optionally further substituted with        1 to 3 R^(x).    -   Embodiment I. A compound of Embodiment H wherein    -   R¹ is phenyl, pyridinyl, thiazolyl, oxazolyl or oxadiazolyl,        each being substituted with one R³, and optionally further        substituted with 1 to 3 R^(x).    -   Embodiment J. A compound of Embodiment 1 wherein    -   R³ is R^(3b) or R^(3e)    -   Embodiment K. A compound of Formula 1 wherein    -   X¹ is CR¹ and X² is CH; or X¹ is CH and X² is CR¹;    -   R¹ is phenyl, pyridinyl, thiazolyl, oxazolyl or thiadizolyl,        each being substituted with one R³, and optionally further        substituted with 1 to 3 R^(x);    -   each R² is independently H; and    -   R³ is R^(3b) or R^(3e).    -   Embodiment L. A compound of Formula 1 wherein    -   X¹ is CR¹ and X² is CH; or X¹ is CH and X² is CR¹;    -   R¹ is phenyl, 4-pyridinyl, 2-thiazolyl, 2-oxazolyl or        2-oxadiazolyl, each being substituted with one R³, and        optionally further substituted with 1 to 3 R^(x);    -   each R² is independently H; and    -   R³ is R^(3b) or R^(3e).    -   Embodiment M. A compound of Formula 1 wherein    -   X¹ is CR¹ and X² is CH; or X¹ is CH and X² is CR¹;    -   X³ is CH;    -   R¹ is phenyl, 4-pyridinyl, 2-thiazolyl, 2-oxazolyl or        2-oxadiazolyl, each being substituted with one R³, and        optionally further substituted with 1 to 3 R^(x);    -   each R² is independently H; and    -   R³ is R^(3b) or R^(3e).    -   Embodiment N. A compound of Formula 1 wherein    -   X¹ is CR¹ and X² is CH; or X¹ is CH and X² is CR¹;    -   X³ is CH;    -   R¹ is phenyl, 4-pyridinyl, 2-thiazolyl, 2-oxazolyl or        2-oxadiazolyl, each being substituted with one R³, and        optionally further substituted with 1 to 3 R^(x);    -   each R² is independently H;    -   R³ is R^(3b) or R^(3e); and    -   R⁴ and R⁵ are each H, or are each methyl, or are taken together        with the carbon atom to which they are attached to form a        cyclopropane ring.

Specific embodiments include compounds of Formula 1 selected from thegroup consisting of (compound numbers refer to Index Tables A-G):compound 11, compound 12, compound 20, compound 24, compound 25,compound 26, compound 30, compound 31, compound 47, compound 56,compound 59, compound 62, compound 64, compound 65, compound 66,compound 71, compound 72, compound 85, compound 86, compound 87,compound 102, compound 139, compound 146, compound 155, compound 156,compound 158, compound 161 and compound 162.

Specific embodiments also include compounds of Formula 1 selected fromthe group consisting of (compound numbers refer to Index Tables A-G):compound 11, compound 12, compound 20, compound 24, compound 25,compound 26, compound 30, compound 31, compound 47, compound 56,compound 59, compound 62, compound 64, compound 65, compound 66,compound 71 and compound 72.

Specific embodiments also include compounds of Formula 1 selected fromthe group consisting of (compound numbers refer to Index Tables A-G):compound 85, compound 86, compound 87, compound 102, compound 139,compound 146, compound 155, compound 156, compound 158, compound 161 andcompound 162.

Of note is that compounds of this invention are characterized byfavorable metabolic and/or soil residual patterns and exhibit activitycontrolling a spectrum of agronomic and nonagronomic invertebrate pests.

Of particular note, for reasons of invertebrate pest control spectrumand economic importance, protection of agronomic crops from damage orinjury caused by invertebrate pests by controlling invertebrate pestsare embodiments of the invention. Compounds of this invention because oftheir favorable translocation properties or systemicity in plants alsoprotect foliar or other plant parts which are not directly contactedwith a compound of Formula 1 or a composition comprising the compound.

Also noteworthy as embodiments of the present invention are compositionscomprising a compound of any of the preceding Embodiments, as well asany other embodiments described herein, and any combinations thereof,and at least one additional component selected from the group consistingof a surfactant, a solid diluent and a liquid diluent, said compositionsoptionally further comprising at least one additional biologicallyactive compound or agent.

Further noteworthy as embodiments of the present invention arecompositions for controlling an invertebrate pest comprising a compoundof any of the preceding Embodiments, as well as any other embodimentsdescribed herein, and any combinations thereof, and at least oneadditional component selected from the group consisting of a surfactant,a solid diluent and a liquid diluent, said compositions optionallyfurther comprising at least one additional biologically active compoundor agent. Embodiments of the invention further include methods forcontrolling an invertebrate pest comprising contacting the invertebratepest or its environment with a biologically effective amount of acompound of any of the preceding Embodiments (e.g., as a compositiondescribed herein).

Embodiments of the invention also include a composition comprising acompound of any of the preceding Embodiments, in the form of a soildrench liquid formulation. Embodiments of the invention further includemethods for controlling an invertebrate pest comprising contacting thesoil with a liquid composition as a soil drench comprising abiologically effective amount of a compound of any of the precedingEmbodiments.

Embodiments of the invention also include a spray composition forcontrolling an invertebrate pest comprising a biologically effectiveamount of a compound of any of the preceding Embodiments and apropellant. Embodiments of the invention further include a baitcomposition for controlling an invertebrate pest comprising abiologically effective amount of a compound of any of the precedingEmbodiments, one or more food materials, optionally an attractant, andoptionally a humectant. Embodiments of the invention also include adevice for controlling an invertebrate pest comprising said baitcomposition and a housing adapted to receive said bait composition,wherein the housing has at least one opening sized to permit theinvertebrate pest to pass through the opening so the invertebrate pestcan gain access to said bait composition from a location outside thehousing, and wherein the housing is further adapted to be placed in ornear a locus of potential or known activity for the invertebrate pest.

Embodiments of the invention also include methods for protecting a seedfrom an invertebrate pest comprising contacting the seed with abiologically effective amount of a compound of any of the precedingEmbodiments.

Embodiments of the invention also include methods for protecting ananimal from an invertebrate parasitic pest comprising administering tothe animal a parasiticidally effective amount of a compound of any ofthe preceding Embodiments.

Embodiments of the invention also include methods for controlling aninvertebrate pest comprising contacting the invertebrate pest or itsenvironment with a biologically effective amount of a compound ofFormula 1, an N-oxide or a salt thereof, (e.g., as a compositiondescribed herein), provided that the methods are not methods of medicaltreatment of a human or animal body by therapy.

This invention also relates to such methods wherein the invertebratepest or its environment is contacted with a composition comprising abiologically effective amount of a compound of Formula 1, an N-oxide ora salt thereof, and at least one additional component selected from thegroup consisting of surfactants, solid diluents and liquid diluents,said composition optionally further comprising a biologically effectiveamount of at least one additional biologically active compound or agent,provided that the methods are not methods of medical treatment of ahuman or animal body by therapy.

The compounds of Formula 1 can be prepared by one or more of thefollowing methods and variations as described in Schemes 1-9. Thedefinitions of substituents in the compounds of Formulae 1-15 below areas defined above in the Summary of the Invention unless otherwise noted.Compounds of Formulae 1a-1f are subsets of the compounds of Formula 1,and all substituents for Formulae 1a-1f are as defined above forFormula 1. The following abbreviations are used: THF is tetrahydrofuran,DMF is N,N-dimethylformamide, NMP is N-methylpyrrolidinone, DCC isN,N′-dicyclohexylcarbodiimide, HATU is1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium3-oxid hexafluoro-phosphate, Tf is trifluoromethane sulfonate, Nf isnonafluorobutane sulfonate, Pd(OAc)₂ is palladium(II) acetate, Pd₂(dba)₃is tris(dibenzylideneacetone) dipalladium(0), PPh₃ is triphenylphospine,PCy₃ is tricyclohexylphosphine, Pt-Bu₃ is tri-tert-butylphosphine,x-phos is 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl,xantphos is 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, s-phos is2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, and dppf is[1,1′-bis(diphenylphosphino)ferrocene]-dichloropalladium(II).

Compounds of Formula 1 can be prepared from compounds of Formula 2a bythe method shown in Scheme 1, in which a compound of Formula 2a istreated with an azide reagent (for example, sodium azide ortetrabutylammonium azide). Typical reaction solvents include DMF or NMP,and typical reaction temperatures range from 80° C. to the boiling pointof the solvent.

Compounds of Formula 1 can also be prepared from compounds of Formula 2bby the method shown in Scheme 2, in which a compound of Formula 2b istreated with triethyl phosphite.

Compounds of Formulae 2a and 2b are Schiff bases and can be prepared bymethods known in the art (see, for example, March, J., Advanced OrganicChemistry, Wiley, 1992, pages 896-898.

Compounds of Formula 1 can also be prepared by the method shown below inScheme 3. In this method, the pyridine or pyrimidine of Formula 4 istreated with a compound of Formula 3 under metal-mediated couplingconditions to provide compounds of Formula 1. For a representativerhodium-catalyzed method, see Organic Letters 2013, 15(6), pages1290-1293; for representative copper-catalyzed methods, see AppliedCatalysis, A: General 2011, 403(1-2), pages 104-111; and Journal ofMolecular Catalysis A: Chemical 2006, 256(1-2), pages 256-260.

Compounds of Formula 1a can be prepared as shown in Scheme 4 by thecoupling of a compound of Formula 5 (wherein LG is a suitable leavinggroup such as Cl, Br, I, Tf or Nf) with a heterocyclic compounds ofFormula 6 (wherein M is a suitable metal or metalloid such as a Mg, Znor B species) in the presence of a catalyst and an appropriate ligand.Appropriate catalysts can be generated from transition metals such as Pd(for example Pd(OAc)₂ or Pd₂(dba)₃ and mono- or bi-dentate ligands suchas PPh₃, PCy₃, Pt-Bu₃, x-phos, xantphos, s-phos, and dppf. Appropriatecatalysts can be generated from transition metals such as Pd (forexample Pd(OAc)₂ or Pd₂(dba)₃ and mono- or bi-dentate ligands such asPPh₃, PCy₃, Pt-Bu₃, x-phos, xantphos, s-phos, and dppf. Typical solventsinclude THF, dioxane, toluene, ethanol, DMF, water or mixtures thereof.Typical reaction temperatures range from ambient temperature to theboiling point of the solvent.

Alternatively, compounds of Formula 1a can also be prepared by thecoupling of a compound of Formula 7 (wherein M is a suitable metal ormetalloid such as a Mg, Zn or B species) with a heterocyclic compound ofFormula 8 (wherein LG is a suitable leaving group such as Cl, Br, I, Tfor Nf) in the presence of a catalyst, an appropriate ligand, and a base.Appropriate catalysts can be generated from transition metals such as Pd(for example Pd(OAc)₂ or Pd₂(dba)₃ and mono- or bi-dentate ligands suchas PPh₃, PCy₃, Pt-Bu₃, x-phos, xantphos, s-phos, and dppf. Typical basesused include carbonates such as sodium carbonate or cesium carbonate,phosphates such as potassium triphosphate, amines such asethyldiisopropylamine, or alkoxides such as sodium tert-butoxide.Typical solvents include THF, dioxane, toluene, ethanol, DMF, water ormixtures thereof. Typical reaction temperatures range from ambienttemperature to the boiling point of the solvent.

Compounds of Formulae 5 and 8 wherein LG is halogen can be prepared fromthe corresponding amines by treatment with a source of ON⁺ such asisoamyl nitrite, t-butyl nitrite or nitrous acid in the presence of ahalogen source such as CuBr₂ or BnNEt₃ ⁺Br⁻. Typical reaction conditionsinclude aqueous or organic solvents such as THF or acetonitrile, andreaction temperatures ranging from 0° C. to the boiling point of thesolvent.

Compounds of Formula 1 wherein X¹ or X² is CR¹ and R¹ is a heterocyclecan be prepared by constructing the heterocycle in the final step. Forexample, in the method shown in Scheme 6, the R¹ group is a thiazolering which can be prepared by reacting the bromoketone of Formula 9 withthe thioamide of Formula 5 under basic conditions to form the compoundof Formula 1b. Typical bases used in this method include carbonates suchas sodium carbonate or cesium carbonate, phosphates such as potassiumtriphosphate, amines such as ethyldiisopropylamine, or alkoxides such assodium tert-butoxide. Typical solvents include THF, dioxane, toluene,ethanol, DMF, water or mixtures thereof. Typical reaction temperaturesrange from ambient temperature to the boiling point of the solvent.

Oxadiazole compounds of Formula 1c and thiadiazole compounds of Formula1d can be prepared from the intermediate of Formula 11 as shown inScheme 7. For example, dehydration of the compound of Formula 11generates the compound of Formula 1c. Typical dehydration reagents usedin the preparation of the compound of Formula 1c include TsCl/TEA andPOCl₃. Similarly, treatment of the intermediate of Formula 11 with athiation reagent results in cyclization to generate the compound ofFormula 1d. Typical thiation reagents used include Lawesson's reagent orP₂S₅. In this method, typical solvents include THF, dioxane, toluene ordichloromethane. Typical reaction temperatures range from ambienttemperature to the boiling point of the solvent.

Compounds of Formula 1e (compounds of Formula 1 wherein the R¹ ring issubstituted with R^(3b)) can be prepared as shown in Scheme 8 byreaction of an amine of Formula 13 with a carboxylic acid of Formula 12in the presence of an amide coupling reagent such as DCC or HATU. Forrepresentative reagents and reaction conditions, see Jones, J. TheChemical Synthesis of Peptides, International Series of Monographs onChemistry, Oxford University: Oxford, 1994.

Compounds of Formula 1f (compounds of Formula 1 wherein the R¹ ring issubstituted with R^(3e)) can be prepared as shown in Scheme 9. In thismethod, a compound of Formula 14 is coupled with a compound of Formula15, optionally followed by further derivatization of the R group, suchas hydrolysis, esterification or amidation.

It is recognized that some reagents and reaction conditions describedabove for preparing compounds of Formula 1 may not be compatible withcertain functionalities present in the intermediates. In theseinstances, the incorporation of protection/deprotection sequences orfunctional group interconversions into the synthesis will aid inobtaining the desired products. The use and choice of the protectinggroups will be apparent to one skilled in chemical synthesis (see, forexample, Greene, T. W.; Wuts, P. G. M. Protective Groups in OrganicSynthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art willrecognize that, in some cases, after introduction of the reagentsdepicted in the individual schemes, additional routine synthetic stepsnot described in detail may be needed to complete the synthesis ofcompounds of Formula 1. One skilled in the art will also recognize thatit may be necessary to perform a combination of the steps illustrated inthe above schemes in an order other than that implied by the particularsequence presented to prepare the compounds of Formula 1.

One skilled in the art will also recognize that compounds of Formula 1and the intermediates described herein can be subjected to variouselectrophilic, nucleophilic, radical, organometallic, oxidation, andreduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the artusing the preceding description can utilize the present invention to itsfullest extent. The following Synthesis Examples are, therefore, to beconstrued as merely illustrative, and not limiting of the disclosure inany way whatsoever. Steps in the following Synthesis Examples illustratea procedure for each step in an overall synthetic transformation, andthe starting material for each step may not have necessarily beenprepared by a particular preparative run whose procedure is described inother Examples or Steps. Percentages are by weight except forchromatographic solvent mixtures or where otherwise indicated. Parts andpercentages for chromatographic solvent mixtures are by volume unlessotherwise indicated. ¹H NMR spectra are reported in ppm downfield fromtetramethylsilane; “s” means singlet, “d” means doublet, “t” meanstriplet, “q” means quartet, “m” means multiplet, “dd” means doublet ofdoublets, “dt” means doublet of triplets, “br s” means broad singlet.DMF means N,N-dimethylformamide. Compound numbers refer to Index TablesA-G.

Synthesis Example 1 Preparation of5-[2-(3-pyridinyl)-2H-indazol-5-yl]-N-(2-pyrimidinylmethyl)-4-thiazolecarboxamide(compound 78) Step A: Preparation of5-bromo-N-(2-pyrimidinylmethyl)-4-thiazolecarboxamide

A mixture of 5-bromothiazole-4-carbonyl chloride (0.30 g, 1.3 mmol),pyrimidin-2-ylmethanamine (0.21 g, 1.94 mmol), and trimethylamine (0.52g, 5.1 mmol) in dichloromethane was stirred at room temperature for 18hours. The reaction mixture was then quenched with saturated aqueoussodium bicarbonate solution (20 mL) and dichloromethane (20 mL). Thephases were separated, and the aqueous phase was extracted withdichloromethane (3×20 mL). The combined organic phases were dried withsodium sulfate, concentrated, and purified by column chromatography(silica gel eluted with a gradient of 20% ethyl acetate/hexanes to 100%ethyl acetate) to give the title compound.

Step B: Preparation of2-(3-pyridinyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2H-indazole

5-Bromo-2-(3-pyridinyl)-2H-indazole was prepared according to the methoddescribed in WO 2015/038503. A mixture of this bromide (1.0 g, 3.6mmol), bis(pinacolato)diboron (1.65 g, 6.5 mmol), Pd(dppf)C₁₂ (0.090 g,0.11 mmol), and potassium acetate (1.1 g, 10 mmol) in 1,4-dioxane wasstirred at room temperature for 1.5 hours. The reaction mixture was thenfiltered through a pad of Celite®, and concentrated under reducedpressure to remove 1,4-dioxane. The residue was purified by MPLC columnchromatography (silica gel eluted with a gradient of 0 to 50% ethylacetate in hexanes) to obtain the title compound, which was useddirectly for the next step.

Step C: Preparation of5-[2-(3-pyridinyl)-2H-indazol-5-yl]-N-(2-pyrimidinylmethyl)-4-thiazolecarboxamide

A mixture of the bromide prepared in Step A (0.13 g, 0.43 mmol), theborate prepared in Step B (0.14 g, 0.44 mmol), Pd(dppf)Cl₂ (0.010 g,0.012 mmol), and potassium carbonate (0.18 g, 1.3 mmol) in dioxane-water(4:1) was purged with nitrogen gas. The mixture was then heated to 100°C. under nitrogen for 18 hours. The reaction mixture was thenconcentrated, and the residue was purified by MPLC column chromatography(silica gel eluted with a mixture of 40% acetone in dichloromethane) togive the desired product. This product was tritrated with diethyl etherand stored in a freezer to give the title compound (52 mg), a compoundof this invention, as a crystalline solid.

Synthesis Example 2 Preparation of2-methyl-N-[[5-[2-(3-pyridinyl)-2H-indazol-5-yl]-1,3,4-oxadiazol-2-yl]carbonyl]alaninemethyl ester (compound 105) Step A: Preparation of2-(3-pyridinyl)-2H-indazole-5-carboxylic acid2-[(1,1-dimethylethoxy)carbonyl]hydrazide

This compound was prepared by the method disclosed in WO 2015/038503 forthe synthesis of methyl2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylate(compound 42 in WO 2015/038503).

Step B: Preparation of ethanedioic acid 1-ethyl ester2-[2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazide]

2-(3-pyridinyl)-2H-indazole-5-carboxylic acid2-[(1,1-dimethylethoxy)carbonyl]-hydrazide prepared in Step A (90 g, 255mmol) was mixed with 1,4-dioxane-hydrogen chloride (4 N, 100 mL) at 0°C. The resulting mixture was stirred and warmed up to room temperaturefor 30 minutes, and maintained at room temperature for an additional 2hours. The reaction mixture was then concentrated under reduced pressureto dryness to yield 62 g of the crude hydrazide-hydrogen chloride salt.A portion of this material (13 g, 44.9 mmol) was mixed with ethyl2-chloro-2-oxo-acetate (8.3 g, 67.7 mmol) and triethylamine (18.1 g,179.6 mmol) in dichloromethane (120 mL) and DMF (60 mL). The resultingmixture was stirred and warmed up to room temperature for 30 minutes,and maintained at room temperature for an additional 16 hours. Thereaction mixture was then concentrated under reduced pressure to drynessto yield the title compound (11.2 g, 31.7 mmol, 70.6%).

Step C: Preparation of ethyl5-[2-(3-pyridinyl)-2H-indazol-5-yl]-1,3,4-oxadiazole-2-carboxylate

Ethanedioic acid 1-ethyl ester2-[2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazide]oxo-acetateprepared in Step B (11.0 g, 31.15 mmol) was mixed with 4-toluenesulfonylchloride (5.94 g, 31.15 mmol) and triethylamine (6.29 g, 62.3 mmol) indichloromethane (100 mL) and DMF (100 mL) at 0° C. The resulting mixturewas stirred and warmed up to room temperature for 1 hour, and maintainedfor at room temperature for an additional 15 hours. The reaction mixturewas then concentrated under reduced pressure to provide a solid. Thecrude solid was purified by silica gel chromatography (0-100% ethylacetate/hexanes) to yield the title compound (8.5 g, 25.3 mmol, 81.4%).

Step D: Preparation of2-methyl-N-[[5-[2-(3-pyridinyl)-2H-indazol-5-yl]-1,3,4-oxadiazol-2-yl]carbonyl]alaninemethyl ester

Ethyl 5-[2-(3-pyridinyl)-2H-indazol-5-yl]-1,3,4-oxadiazole-2-carboxylateprepared in Step C (3.0 g, 8.95 mmol) was mixed with lithium hydroxide(0.32 g, 13.4 mmol) in THF (10 mL) and water (5 mL) at 0° C. Theresulting mixture was stirred and warmed up to room temperature for 1hour, and maintained at room temperature for an additional 3 hours. Thereaction mixture was then concentrated under reduced pressure to providethe crude acid. A mixture of this crude acid, methyl2-amino-2-methyl-propanoate (1.26 g, 10.74 mmol), HATU (5.1 g, 13.43mmol) and DIPEA (2.9 g, 22.4 mmol) in DMF (10 mL) was stirred at roomtemperature for 16 hours. A precipitate formed which was collected viasuction filtration. The collected solid was washed with EtOAc, then withwater, and finally dried in a vacuum oven to yield the title compound, acompound of this invention as a white solid (1.5 g, 3.69 mmol, 41.2%).

Synthesis Example 3 Preparation of2-methyl-N-[[5-[2-(3-pyridinyl)-2H-indazol-5-yl]-1,3,4-thiadiazol-2-yl]carbonyl]alaninemethyl ester (compound 128) Step A: Preparation of ethyl5-[2-(3-pyridinyl)-2H-indazol-5-yl]-1,3,4-thiadiazole-2-carboxylate

Ethanedioic acid 1-ethyl ester2-[2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazide]oxo-acetateprepared in Synthesis Example 2 Step B (5.0 g, 14.16 mmol) was mixedwith Lawesson's Reagent (5.73 g, 14.16 mmol) in toluene (30 mL) at roomtemperature The resulting mixture was stirred and heated to 111° C., andmaintained at this temperature for 2 hours. The suspension was thencooled, passed through a short pad of silica gel, and washed with 100 mLof ethyl acetate to provide the title compound as pale yellow solid (3.0g, 8.54 mmol, 60.3%).

Step B: Preparation of2-methyl-N-[[5-[2-(3-pyridinyl)-2H-indazol-5-yl]-1,3,4-thiadiazol-2-yl]carbonyl]alaninemethyl ester

The title compound was prepared by the same method as described forSynthesis Example 2 Step D.

Synthesis Example 4 Preparation ofN-(2,2-dimethoxyethyl)-3-[2-(3-pyridinyl)-2H-indazol-5-yl]benzamide(compound 25) Step A: Preparation of methyl3-[2-(3-pyridinyl)-2H-indazol-5-yl]benzoate

A mixture of 5-bromo-2-(3-pyridinyl)-2H-indazole (3.4 g, 11.64 mmol),(3-methoxycarbonylphenyl)boronic acid (2.55 g, 14.2 mmol) and potassiumphosphate (3.0 g, 14.2 mmol) in DMF (60 mL) was degassed using nitrogenfor 15 minutes. Pd(PPh₃)₄ was then added, and the reaction mixture wasstirred at 100° C. overnight. Water was then added, and the reactionmixture was extracted three times with EtOAc. The combined organicextracts were washed with saturated aqueous NaCl and dried overanhydrous Na₂SO₄. After evaporation of the solvent under reducedpressure, the residue was purified by MPLC (40 g silica, 15-60% EtOAc inhexanes) to yield the title compound (3.0 g) as a white solid. ¹H NMR(500 MHz, DMSO-d₆): δ ppm 9.35 (br s, 1H), 9.25 (s, 1H), 8.66 (d, J=3.91Hz, 1H), 8.45-8.57 (m, 1H), 8.21-8.29 (m, 1H), 8.09 (s, 1H), 8.01 (d,J=7.83 Hz, 1H), 7.94 (d, J=7.83 Hz, 1H), 7.85 (d, J=8.80 Hz, 3H),7.57-7.72 (m, 3H), 3.89 (s, 3H).

Step B: Preparation of 3-[2-(3-pyridinyl)-2H-indazol-5-yl]benzoic acid

To a stirred suspension of methyl3-[2-(3-pyridyl)-2H-indazol-5-yl]benzoate (2.9 g, 8.35 mmol) in MeOH/THF(30 mL/30 mL) was added 2 M sodium hydroxide (10 mL), and the suspensionwas heated at 70° C. for 2 hours. The reaction mixture was then cooledto room temperature and concentrated under reduced pressure. Theresulting residue was diluted with water and acidified with 2 Mhydrochloric acid to pH ˜4. This mixture was then heated to reflux for30 minutes, and then cooled. The precipitated solid was collected byfiltration and dried to yield the title compound as white solid (2.5 g).¹H NMR (500 MHz, DMSO-d₆): δ ppm 9.34 (d, J=2.45 Hz, 1H), 9.24 (s, 1H),8.65 (dd, J=4.65, 1.22 Hz, 1H), 8.44-8.54 (m, 1H), 8.24 (t, J=1.71 Hz,1H), 8.08 (s, 1H), 7.89-8.01 (m, 1H), 7.85 (d, J=9.29 Hz, 2H), 7.55-7.74(m, 3H).

Step C: Preparation ofN-(2,2-dimethoxyethyl)-3-[2-(3-pyridinyl)-2H-indazol-5-yl]benzamide

T₃P (280 μL, 0.47 mmol, 50 wt % in EtOAc) was added to a stirredsuspension of 3-[2-(3-pyridyl)-2H-indazol-5-yl]benzoic acid (100 mg,0.31 mmol), 2,2-dimethoxyethanamine (50 μL, 0.47 mmol) and triethylamine (90 μL, 0.62 mmol) in dry dichloromethane (5 mL) under a nitrogenatmosphere. After stirring the reaction mixture at room temperatureovernight, dichloromethane (20 mL) was added, the resulting solution waswashed with water, and the organic phase was dried over Na₂SO₄. Thedried solution was concentrated under reduced pressure to provide asolid which was triturated with 1:1 ether/hexane, and further washedwith 1:1 ether/hexane to yield the title compound, a compound of thisinvention, as a white solid (100 mg). ¹H NMR (500 MHz, DMSO-d₆): δ ppm9.19-9.29 (m, 1H), 8.64-8.74 (m, 1H), 8.53 (s, 1H), 8.31-8.40 (m, 1H),8.09 (s, 1H), 7.93 (s, 1H), 7.87 (d, J=8.80 Hz, 1H), 7.70-7.82 (m, 2H),7.65 (d, J=1.47 Hz, 1H), 7.54 (d, J=7.34 Hz, 2H), 6.36-6.48 (m, 1H),4.53 (m, 1H), 3.66 (t, J=5.62 Hz, 2H), 3.46 (m, 6H).

Synthesis Example 5 Preparation ofN-(2-hydroxyethyl)-3-[2-(3-pyridinyl)-2H-indazol-5-yl]benzamide(compound 31) Step A: Preparation ofN-(2-hydroxyethyl)-3-[2-(3-pyridinyl)-2H-indazol-5-yl]benzamide

DIPEA (880 μL, 5.07 mmol) was added to a stirred suspension of3-[2-(3-pyridyl)-2H-indazol-5-yl]benzoic acid (200 mg, 0.63 mmol) andHATU (290 mg, 0.76 mmol) in DMF (3 mL). The mixture was stirred at roomtemperature for 1 hour, 2-aminoethanol (200 μL, 3.17 mmol) was added,and the reaction mixture was stirred overnight. The reaction mixture wasconcentrated under reduced pressure, and the resulting residue wasredissolved in methanol (˜2 mL) and diluted with water. The precipitatedproduct was collected by filtration and dried under reduced pressure toyield the title compound, a compound of this invention, as white solid(170 mg). ¹H NMR (500 MHz, DMSO-d₆): δ ppm 9.36 (d, J=2.45 Hz, 1H), 9.26(s, 1H), 8.66 (dd, J=4.65, 1.22 Hz, 1H), 8.57-8.64 (s, 2H), 8.20 (s,1H), 8.11 (s, 1H), 7.80-7.93 (m, 3H), 7.75 (dd, J=9.05, 1.71 Hz, 1H),7.65 (dd, J=8.31, 4.89 Hz, 1H), 7.51-7.59 (m, 1H), 4.71 (m, 1H), 3.54(d, J=5.87 Hz, 2H) 3.36-3.38 (m, 2H).

Synthesis Example 6 Preparation ofN-[1-[(methylamino)carbonyl]cyclopropyl]-4-[2-(3-pyridinyl)-2H-indazol-5-yl]-2-pyridinecarboxamide(compound 85) Step A: Preparation of2-(3-pyridinyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2H-indazole

A mixture of 5-bromo-2-(3-pyridyl)-2H-indazole (3 g, 10.9 mmol),4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane(5.5 g, 21.8 mmol) and potassium acetate (3.6 g, 33.0 mmol) in dioxane(35 mL) was degassed using nitrogen for 15 minutes. Pd(dppf)C₁₂ was thenadded, and the reaction mixture was stirred and heated to refluxovernight. The reaction mixture was then allowed to cool to roomtemperature and was filtered through a Celite® plug. The filtrate wasconcentrated under reduced pressure, and the resulting residue waspurified by MPLC (40 g silica, 25-60% EtOAc in hexanes) to yield thetitle compound (2.1 g) as a light brown solid. ¹H NMR (500 MHz, CDCl₃):δ ppm 9.21 (br s, 1H), 8.58-8.81 (m, 1H), 8.48 (s, 1H), 8.30-8.25 (m,2H), 7.73 (d, J=9.29 Hz, 2H), 7.30-7.55 (m, 1H), 1.38 (s, 12H).

Step B: Preparation of4-[2-(3-pyridinyl)-2H-indazol-5-yl]-2-pyridinecarboxylic acid

A mixture of2-(3-pyridinyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2H-indazole(400 mg, 1.2 mmol), methyl 4-bromopyridine-2-carboxylate (300 mg, 1.36mmol) and potassium carbonate (2M aqueous solution; 1.2 mL, 2.4 mmol) inDMF (6 mL) was degassed using nitrogen for 10 minutes. Pd(PPh₃)₄ wasthen added, and the reaction mixture was stirred and heated to 100° C.for 15 hours. The reaction mixture was then cooled to room temperatureand diluted with acetone (˜10 mL). Upon addition of acetone, a solid wasformed which was then collected by filtration. This solid wasredissolved in water and acidified with 1 M hydrochloric acid to pH ˜4.The precipitated product was collected by filtration and dried underreduced pressure to yield the title compound (350 mg) as tan whitesolid. LC-MS (ES+) [M+H]⁺=317.3.

Step C: Preparation of methyl1-[[[4-[2-(3-pyridinyl)-2H-indazol-5-yl]-2-pyridinyl]carbonyl]amino]cyclopropanecarboxylate

Methyl 1-aminocyclopropanecarboxylate hydrochloride (40 mg, 0.27 mmol)was added to a stirred suspension of4-[2-(3-pyridinyl)-2H-indazol-5-yl]-2-pyridinecarboxylic acid (70 mg,0.22 mmol) and HATU (100 mg, 0.26 mmol) in DMF (4 mL). The reactionmixture was stirred at room temperature for 1 hour, DIPEA (115 μL, 0.66mmol) was added, and stirring was continued overnight. The reactionmixture was then concentrated under reduced pressure, and the residuewas purified by MPLC (12 g silica, 0-10% MeOH in dichloromethane) toobtain the title compound (80 mg) as white solid. ¹H NMR (500 MHz,DMSO-d₆): δ ppm 9.29-9.45 (m, 2H), 8.64-8.77 (m, 2H), 8.49-8.59 (m, 1H),8.31-8.40 (m, 1H), 8.09-8.22 (m, 1H), 7.98-8.07 (m, 1H), 7.88-7.96 (m,1H), 7.79-7.87 (m, 1H), 7.62-0.72 (m, 1H), 3.66 (s, 3H), 1.42-1.54 (m,2H), 1.23-1.28 (m, 2H).

Step D: Preparation of1-[[[4-[2-(3-pyridinyl)-2H-indazol-5-yl]-2-pyridinyl]carbonyl]amino]cyclopropanecarboxylicacid

To a stirred suspension of methyl1-[[[4-[2-(3-pyridinyl)-2H-indazol-5-yl]-2-pyridinyl]carbonyl]amino]cyclopropanecarboxylate(260 mg, 0.63 mmol) in MeOH/THF (5 mL/5 mL) was added 2 M sodiumhydroxide (5 mL), and the reaction mixture was heated to 65° C. for 2hours. The reaction mixture was then cooled to room temperature andconcentrated under reduced pressure. The residue was diluted with water,acidified with 2 M hydrochloric acid to pH ˜4, and then heated to refluxfor 30 minutes. After cooling, the precipitated product was collected byfiltration and dried under reduced pressure to yield the title compound(240 mg) as white solid. LC-MS (ES−) [M−H]⁻=398.2.

Step E: Preparation ofN-[1-[(methylamino)carbonyl]cyclopropyl]-4-[2-(3-pyridinyl)-2H-indazol-5-yl]-2-pyridinecarboxamide

Triethylamine (140 μL, 1.0 mmol) was added to a stirred suspension of1-[[[4-[2-(3-pyridinyl)-2H-indazol-5-yl]-2-pyridinyl]carbonyl]amino]cyclopropanecarboxylicacid (80 mg, 0.2 mmol), methylamine hydrochloride (54 mg, 0.8 mmol) andHATU (90 mg, 0.24 mmol) in DMF (3 mL). The reaction mixture was thenstirred at room temperature overnight. The reaction mixture was thencooled and concentrated under reduced pressure. The resulting residuewas redissolved in methanol (˜2 mL) and diluted with water. Theprecipitated solid was collected by filtration and dried under reducedpressure to yield the title compound, a compound of this invention, aswhite solid (78 mg). ¹H NMR (500 MHz, DMSO-d₆): δ ppm 9.31-9.41 (m, 2H),9.17-9.24 (m, 1H), 8.67-8.75 (m, 2H), 8.49-8.58 (m, 1H), 8.31-8.41 (m,2H), 7.99-8.07 (m, 1H), 7.88-7.96 (m, 1H), 7.80-7.88 (m, 1H), 7.73-7.80(m, 1H), 7.63-7.71 (m, 1H), 2.54-2.63 (m, 3H), 1.32-1.41 (m, 2H),1.01-1.10 (m, 2H).

Synthesis Example 7 Preparation ofN-[1-(aminocarbonyl)cyclopropyl]-4-[2-(3-pyridinyl)-2H-indazol-5-yl]-2-pyridinecarboxamide(compound 86) Step A: Preparation ofN-[1-(aminocarbonyl)cyclopropyl]-4-[2-(3-pyridinyl)-2H-indazol-5-yl]-2-pyridinecarboxamide

Triethylamine (140 μL, 1.0 mmol) was added to a stirred suspension of1-[[[4-[2-(3-pyridinyl)-2H-indazol-5-yl]-2-pyridinyl]carbonyl]amino]cyclopropanecarboxylicacid (80 mg, 0.2 mmol), ammonium chloride (53 mg, 1.0 mmol) and HATU (90mg, 0.24 mmol) in DMF (3 mL). The reaction mixture was then stirred atroom temperature overnight. The reaction mixture was then cooled andconcentrated under reduced pressure. The resulting residue wasredissolved in methanol (˜2 mL) and diluted with water. The precipitatedsolid was collected by filtration and dried under reduced pressure toyield the title compound, a compound of this invention, as a white solid(70 mg). ¹H NMR (500 MHz, DMSO-d₆): δ ppm 9.29-9.42 (m, 2H), 9.2 (s,1H), 8.64-8.74 (m, 2H), 8.49-8.60 (m, 1H), 8.29-8.38 (m, 2H), 7.97-8.04(m, 1H), 7.89-7.96 (m, 1H), 7.78-7.86 (m, 1H), 7.63-7.73 (m, 1H), 7.24(br s, 1H), 7.01 (br s, 1H), 1.30-1.41 (m, 2H), 1.01-1.12 (m, 2H).

Synthesis Example 8 Preparation ofN-[1-[(dimethylamino)carbonyl]cyclopropyl]-4-[2-(3-pyridinyl)-2H-indazol-5-yl]-2-pyridinecarboxamide(compound 87) Step A: Preparation ofN-[1-[(dimethylamino)carbonyl]cyclopropyl]-4-[2-(3-pyridinyl)-2H-indazol-5-yl]-2-pyridinecarboxamide

Dimethylamine (0.5 mL, 1.0 mmol; 2M in THF) was added to a stirredsuspension of1-[[4-[2-(3-pyridyl)-2H-indazol-5-yl]pyridine-2-carbonyl]amino]cyclopropanecarboxylicacid (80 mg, 0.2 mmol) and HATU (90 mg, 0.24 mmol) in DMF (3 mL). Thereaction mixture was then stirred at room temperature overnight. Thereaction mixture was then concentrated under reduced pressure, and theresidue was purified by MPLC (24 g silica, 0-10% MeOH indichloromethane) to yield the title compound, a compound of thisinvention, as white solid (78 mg). ¹H NMR (500 MHz, DMSO-d₆): δ ppm 9.46(s, 1H), 9.30-9.40 (m, 2H), 8.65-8.75 (m, 2H), 8.47-8.58 (m, 1H),8.28-8.39 (m, 2H), 7.98-8.07 (m, 1H), 7.88-7.95 (m, 1H), 7.77-7.86 (m,1H), 7.61-7.74 (m, 1H), 2.90 (br s, 6H), 1.22-1.32 (m, 2H), 1.06-1.17(m, 2H).

Synthesis Example 9 Preparation of2-[2-(3-pyridinyl)-2H-indazol-5-yl]-N-(tetrahydro-2H-pyran-4-yl)-4-thiazolecarboxamide(compound 64) Step A: Preparation of2-[2-(3-pyridinyl)-2H-indazol-5-yl]-4-thiazolecarboxylate

2-(3-Pyridinyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2H-indazole(563 mg, 1.75 mmol, prepared by the method of Synthesis Example 6 StepA) was added to a solution of 2-bromothiazole-4-carboxylic acid methylester (300 mg, 1.35 mmol) in toluene:methanol (8:2 ratio, 10 mL),followed by the addition of potassium acetate (399 mg, 4.05 mmol). Thereaction mixture was purged with nitrogen gas for 5 minutes. Pd(dba)₃(62 mg, 0.067 mmol) and Pd(PPh₃)C₁₂ (47 mg, 0.067 mmol) were added, andthe reaction mixture was purged again with nitrogen gas. The reactionmixture was then heated to reflux, and kept at reflux overnight. Thereaction mixture was then cooled and concentrated under reducedpressure. The residue was extracted with ethyl acetate, and the organicextracts were concentrated under reduced pressure. This residue waspurified by column chromatography (30% EtOAc in petroleum ether) toobtain the title compound (260 mg) as a solid. ¹H NMR (500 MHz,chloroform-d): 6 ppm 4.00 (s, 2H), 7.31-7.64 (m, 1H), 7.77-7.93 (m, 1H),7.95-8.06 (m, 1H), 8.25-8.35 (m, 1H), 8.40-8.48 (m, 1H), 8.56 (s, 1H),8.63-8.77 (m, 1H), 8.98-9.33 (m, 1H).

Step B: Preparation of2-[2-(3-pyridinyl)-2H-indazol-5-yl]-4-thiazolecarboxylic acid

LiOH-H₂O (250 mg, 5.95 mmol) was added to a solution of2-[2-(3-pyridinyl)-2H-indazol-5-yl]-4-thiazolecarboxylate (250 mg, 0.74mmol) in THF:water (1:1 ratio, 10 mL), and the reaction mixture wasstirred for 8 hours at room temperature. The reaction mixture was thenacidified with 1N HCl to pH 2. After stirring, the precipitated solidwas isolated by filtration and dried under reduced pressure to yield 200mg of the title compound as a solid. ¹H NMR (500 MHz, DMSO-d₆): δ ppm7.53-7.73 (m, 1H), 7.78-7.92 (m, 1H), 7.90-7.99 (m, 1H), 8.36-8.55 (m,1H), 8.60-8.76 (m, 1H), 9.34 (s, 1H).

Step C: Preparation of2-[2-(3-pyridinyl)-2H-indazol-5-yl]-N-(tetrahydro-2H-pyran-4-yl)-4-thiazolecarboxamide

Oxalyl chloride (0.05 mL, 0.646 mmol) was added at 0° C. to a solutionof 2-[2-(3-pyridinyl)-2H-indazol-5-yl]-4-thiazolecarboxylic acid (145mg, 0.432 mmol) in dichloromethane (5 mL), followed by the addition offew drops of dry DMF. The reaction mixture was stirred for 2 h at roomtemperature, and then concentrated under reduced pressure. The resultingresidue was dissolved in dichloromethane, and tetrahydropyran-4-ylamine(0.09 mL, 0.863 mmol) and triethylamine (0.12 mL, 0.863 mmol) wereadded; the reaction mixture was then stirred at room temperature for 12hours. After completion of the reaction, water was added, and thereaction mixture was extracted with dichloromethane. The organicextracts were dried over sodium sulfate and concentrated under reducedpressure. The resulting solid was purified by column chromatography (30%EtOAc in petroleum ether) to yield the title compound, a compound ofthis invention, as a solid (29 mg). ¹H NMR (500 MHz, chloroform-d): δppm 2.00-2.14 (m, 2H), 2.88 (s, 2H), 3.39 (br s, 3H), 3.52-3.65 (m, 1H),3.96 (br s, 4H), 4.14-4.32 (m, 1H), 7.32-7.42 (m, 1H), 7.48-7.56 (m,1H), 7.79-7.91 (m, 1H), 7.94-8.05 (m, 1H), 8.07-8.17 (m, 1H), 8.26-8.41(m, 1H), 8.58 (s, 1H), 8.65-8.76 (m, 1H), 9.06-9.29 (m, 1H).

Synthesis Example 10 Preparation ofN-(1-cyano-1-methylethyl)-2-[2-(3-pyridinyl)-2H-indazol-5-yl]-4-oxazolecarboxamide(compound 155) Step A: Preparation ofN-(1-cyano-1-methylethyl)-2-[2-(3-pyridinyl)-2H-indazol-5-yl]-4-oxazolecarboxamide

The title compound was prepared by a method analogous to the onedescribed in Synthesis Example 9 Steps A-C. ¹H NMR (500 MHz, DMSO-d₆): δppm 1.72 (s, 6H), 7.66 (dd, J=8.31, 4.89 Hz, 1H), 7.85-7.94 (m, 1H),8.00 (dd, J=9.29, 1.47 Hz, 1H), 8.54 (br d, J=16.14 Hz, 3H), 8.68 (dd,J=4.65, 1.22 Hz, 1H), 8.80 (s, 1H), 9.27-9.43 (m, 2H).

Synthesis Example 11 Preparation ofN-methyl-2-[3-[2-(3-pyridinyl)-2H-indazol-5-yl]phenoxy]acetamide(compound 102) Step A: Preparation of3-[2-(3-pyridinyl)-2H-indazol-5-yl]phenol

(3-Hydroxyphenyl)boronic acid (1.2 g, 0.008 mol) was added to5-bromo-2-(3-pyridyl)-2H-indazole (2 g, 0.007 mol) in toluene:ethanol(10 mL: 10 mL). Sodium carbonate solution (2.3 g, 2M, 0.021 mol) wasadded, and the reaction mixture was purged with nitrogen gas for 5minutes. Pd(PPh₃)₄ (421 mg, 0.0003 mol) was then added, and the reactionmixture was purged again with nitrogen for 5 minutes. The reactionmixture was then heated to reflux and stirred at reflux for 2 hours. Thereaction mixture was then cooled and concentrated under reducedpressure. The resulting solid was stirred with ethyl acetate, and thenthe solid was isolated by filtration (1.3 g). This solid was dried underreduced pressure and used directly in the next step. ¹H NMR (500 MHz,DMSO-d₆): δ ppm 6.53-6.83 (m, 1H), 6.99-7.16 (m, 2H), 7.20-7.33 (m, 1H),7.54-7.67 (m, 3H), 7.75-7.87 (m, 1H), 7.89-8.07 (m, 1H), 8.39-8.54 (m,1H), 8.60-8.71 (m, 1H), 9.11-9.25 (m, 1H), 9.29-9.41 (m, 1H), 9.44-9.54(m, 1H).

Step B: Preparation of methyl2-[3-[2-(3-pyridinyl)-2H-indazol-5-yl]phenoxy]acetate

Sodium hydride (167 mg, 0.006 mol) was added at 0° C. to a solution of3-[2-(3-pyridinyl)-2H-indazol-5-yl]phenol (1 g, 0.003 mol) in DMF (2mL). Methyl 2-bromoacetate (639 mg, 0.004 mol) was then slowly added,and the reaction mixture was stirred for 5 hours at room temperature.Water was added, and the reaction mixture was extracted with ethylacetate; the organic phase was separated, dried over sodium sulfate, andconcentrated under reduced pressure. The residue was purified by MPLC(20% EtOAc in petroleum ether) to yield the title compound as a paleyellow solid (1 g). ¹H NMR (500 MHz, chloroform-d): 6 ppm 3.83 (s, 3H),4.72 (s, 2H), 6.82-6.96 (m, 1H), 7.22 (s, 1H), 7.27-7.32 (m, 1H), 7.39(s, 1H), 7.44-7.49 (m, 1H), 7.51-7.56 (m, 1H), 7.59-7.64 (m, 1H),7.65-7.71 (m, 1H), 7.87 (s, 2H), 8.01 (s, 1H), 8.31-8.41 (m, 1H), 8.51(s, 1H), 8.62-8.72 (m, 1H), 9.15-9.27 (m, 1H).

Step C: Preparation of2-[3-[2-(3-pyridinyl)-2H-indazol-5-yl]phenoxy]acetic acid

Methyl 2-[3-[2-(3-pyridinyl)-2H-indazol-5-yl]phenoxy]acetate (1 g, 0.002mol) was dissolved in a solution of methanol (10 mL) and 1N NaOHsolution (10 mL). The reaction mixture was heated to reflux for 2 hours,cooled, and concentrated under reduced pressure. The pH of the resultingresidue was adjusted to pH 4-5 by the addition of 1N HCl, and thisreaction mixture was heated to reflux and stirred at reflux for 1 hour.The reaction mixture was then cooled, and the precipitated solid wasisolated by filtration (850 mg) and dried under reduced pressure. ¹H NMR(500 MHz, DMSO-d₆): δ ppm 4.78 (s, 2H), 6.77-6.94 (m, 1H), 7.18-7.27 (m,1H), 7.29-7.34 (m, 1H), 7.34-7.43 (m, 1H), 7.57-7.71 (m, 3H), 7.73-7.90(m, 1H), 7.94-8.08 (m, 1H), 8.42-8.57 (m, 1H), 8.59-8.73 (m, 1H),9.19-9.29 (m, 1H), 9.30-9.39 (m, 1H).

Step D: Preparation ofN-methyl-2-[3-[2-(3-pyridinyl)-2H-indazol-5-yl]phenoxy]acetamide

HATU (131 mg, 0.34 mmol) was added to a solution of2-[3-[2-(3-pyridinyl)-2H-indazol-5-yl]phenoxy]acetic acid (100 mg, 0.289mmol) in dry DMF (10 mL), and the reaction mixture was stirred for 20minutes; methylamine hydrochloride (97 mg, 1.44 mmol) was then added andthe reaction mixture stirred for 1 hour. DIPEA (0.35 mL, 2.02 mmol) wasadded, and the reaction mixture was stirred at room temperature for 16hours. Water was added, and the reaction mixture was extracted withethyl acetate. The organic phase was separated, dried over sodiumsulfate, and concentrated under reduced pressure. The resulting residuewas purified by column chromatography (5% MeOH in dichloromethane) toobtain the title compound, a compound of this invention, as an off whitesolid (70 mg). ¹H NMR (500 MHz, DMSO-d₆): δ ppm 2.66 (d, J=4.89 Hz, 3H),4.56 (s, 2H), 6.87-7.01 (m, 1H), 7.32 (br d, J=16.14 Hz, 2H), 7.40 (s,1H), 7.61-7.70 (m, 2H), 7.82 (d, J=9.29 Hz, 1H), 8.03 (s, 2H), 8.45-8.53(m, 1H), 8.65 (d, J=4.40 Hz, 1H), 9.25 (s, 1H), 9.35 (d, J=1.96 Hz, 1H).

Specific compounds of Formula 1, prepared by the methods and variationsas described in preceding Schemes 1-9 and Synthesis Examples 1-11, areshown in the Index Tables below. The following abbreviations may beused: Cmpd means Compound, t is tertiary, c is cyclo, Me is methyl, Etis ethyl and Ph is phenyl. A wavy line or “−” in a structure fragmentdenotes the attachment point of the fragment to the remainder of themolecule. The representation “—C(-ring members-)” is used to denote aring in which the first and last ring members are bonded to a singlecarbon atom; for example, “—C(—CH₂CH₂—)CO₂Me” denotes the followingstructure:

The abbreviation “Ex.” stands for “Example” and is followed by a numberindicating in which Synthesis Example the compound is prepared.

INDEX TABLE A-1

Cmpd. R³ position MS No. on ring R³ data 1 2 —C(O)NH(cyclopropyl) 355.42 2 —C(O)NHC(Me)₂CN 382.4 3 2 —C(O)NHCH₂(2-pyrimidinyl) 407.3 4 4—C(O)NH(cyclopropyl) 355.3 5 4 —C(O)NHC(Me)₂CN 382.4 6 4—C(O)NHNHC(O)OMe 388.3 7 4 —C(O)NHCH₂(2-pyrimidinyl) 407.3 8 4—C(O)NHCH₂(tetrahydro-2-furanyl) 399.4

INDEX TABLE A-2

R³ Cmpd position MS No. on ring R³ data   9 4 —C(O)NHC(Me)₂C(O)OMe 415.0 10 4 —C(O)NHC(Me)₂CN 382.4  11 4 —C(O)NHCH₂CH(OMe)₂ 403.4  12 4—C(O)NHCH₂(tetrahydro-2-furanyl) 399.4  13 4 —C(O)NHCH₂(2-pyrimidinyl)407.4  14 4 —C(O)NHNHC(O)OMe 388.3  15 4 —C(O)NHC(Me)₂C(O)N(Me)₂ 428.4 16 4 —C(O)NHC(Me)₂C(O)NHMe 414.4  17 2,4 2-Cl, 4-[—C(O)NH(cyclopropyl)]389  18 2,4 2-Cl, 4-[—C(O)NHCH₂CH(OMe)₂] 437  19 2,4 2-F,4-[—C(O)NH(cyclopropyl)] 373.4  20 2,4 2-F, 4-[—C(O)NHCH₂CH(OMe)₂] 421.4 21 3,4 3-Cl, 4-[—C(O)NH(cyclopropyl)] 389  22 3,4 3-Cl,4-[—C(O)NHCH₂CH(OMe)₂] 437  23 4 —C(O)NHC(—CH₂CH₂—)C(O)OMe 413.4  24 3—C(O)NHC(Me)₂C(O)OMe 415.0  25 3 —C(O)NHCH₂CH(OMe)₂ 403.0  26 3—C(O)NHC(Me)₂C(O)NHMe 414.4  27 4 —C(O)NHC(—CH₂CH₂—)C(O)NHCH₂CH₂OH 442.4 28 4 —C(O)NHC(—CH₂CH₂—)C(O)NHCH₂CH₂OMe 456.4  29 3—C(O)NHC(Me)₂C(O)NHCH₂CH(OMe)₂ 488.5  30 4—C(O)NHC(—CH₂CH₂—)C(O)NHCH₂CH(OMe)₂ 486.3  31 3 —C(O)NHCH₂CH₂OH 359.4 32 3 —C(O)NHC(Me)₂C(O)NHCH₂CH₂OH 444.4  33 3,4 3-F,4-[—C(O)NH(cyclopropyl)] 373.4  34 3,4 3-F, 4-[—C(O)NHCH₂CH(OMe)₂] 421.0101 3 —OCH₂C(O)OMe 360 102 3 —OCH₂C(O)NHMe 359 103 3 —OCH₂C(O)NMe₂ 373104 3 —OCH₂C(O)NHCH₂CF₃ 427 106 3 —OCH₂C(O)NHCH₂CH(OMe)₂ 433 107 3—OCH₂C(O)NHCH₂(2-pyrimidinyl) 437 A is CH; X³ is N  92 3—C(O)NHC(—CH₂CH₂—)C(O)NH₂ 399.1  93 3 —C(O)NHC(—CH₂CH₂—)C(O)NHMe 413.2 94 3 —C(O)NHC(—CH₂CH₂—)C(O)NMe₂ 427.3 A is N; X³ is CH  35 4—C(O)NHC(Me)₂C(O)NMe₂ 429  36 4 —C(O)NHC(Me)₂C(O)OMe 416  37 4—C(O)NHC(Me)₂C(O)OH 402  38 4 —C(O)NHC(—CH₂CH₂—)C(O)OMe 414  39 4—C(O)NHC(Me)₂C(O)NHMe 415  40 4 —C(O)NHC(—CH₂CH₂—)C(O)NHCH₂CH₂OH 443  414 —C(O)NHC(—CH₂CH₂—)C(O)NHMe 413  42 4 —C(O)NHC(Me)₂CH₂OH 388 A is CF;X³ is CH  80 4 —C(O)NHC(Me)₂C(O)NHMe 432  81 4 —C(O)NHC(Me)₂C(O)NMe₂ 446 82 4 —C(O)NHC(Me)₂C(O)NHCH₂CH₂OH 462  83 4 —C(O)NHC(Me)₂C(O)OMe 433 1083 —H₂C(O)OMe 378 163 3 —H₂C(O)NHMe 377 164 3 —OCH₂C(O)NMe₂ 391 165 3—OCH₂C(O)NHCH₂(2-pyrimidinyl) 455 166 3 —OCH₂C(O)NHOMe 393

INDEX TABLE B-1

Cmpd. R³ position MS No. on ring R³ data  43 6 —C(O)NH(cyclopropyl)357.3  44 6 —C(O)NHCH₂(2-pyrimidinyl) 174 5 —OCH₂C(O)NHCH₂CF₃ 428 175 5—OCH₂C(O)NHCH₂CH(OMe)₂ 434 176 5 —OCH₂C(O)OMe 361

INDEX TABLE B-2

R³ Cmpd. position MS No. on ring R³ data  45 6 —C(O)NH(cyclopropyl)356.3  46 6 —C(O)NHCH₂CH(OMe)₂ 404.4  88 5 —C(O)NHC(—CH₂CH₂—)C(O)NH₂399.3  89 5 —C(O)NHC(—CH₂CH₂—)C(O)NHMe 413.3  90 5—C(O)NHC(—CH₂CH₂—)C(O)NMe₂ 427.2 145 6 —OCH₂C(O)NHCH₂CF₃ 428

INDEX TABLE B-3

Cmpd. R³ position MS No. on ring R³ data 85 2 —C(O)NHC(—CH₂CH₂—)C(O)NHMe413.2 86 2 —C(O)NHC(—CH₂CH₂—)C(O)NH₂ 399.1 87 2—C(O)NHC(—CH₂CH₂—)C(O)NMe₂ 427.2

INDEX TABLE C-1

Cmpd. MS No. R³ data 91 —CH₂C(O)Me 346

INDEX TABLE C-2

Cmpd. MS No. R³ data 84 —CH₂C(O)Me 346

INDEX TABLE D

Cmpd. R³ position MS No. on ring R³ data 146 4 —C(O)NHCH₂(2—pyrimidinyl)398 147 4 —C(O)NHOMe 336 154 4 —C(O)NHC(—CH₂CH₂—)C(O)OMe 404 155 4—C(O)NHC(Me)₂CN 373 156 4 —C(O)NHCH₂CN 345 157 4 —C(O)NHCH₂CH₂SMe 380158 4 —C(O)NH(4-morpholino) 390 159 4 —C(O)NH(cyclopropyl) 346 160 4—C(O)NHC(—CH₂CH₂—)C(O)NHMe 403 161 4 —C(O)NHC(—CH₂CH₂—)C(O)NMe₂ 417 1624 —C(O)NHC(—CH₂CH₂—)C(O)NH(isopropyl) 431

INDEX TABLE E-1

Cmpd. R³ position MS No. on ring R³ data 76 4 —C(O)NHCH₂CH(OMe)₂ 410 774 —C(O)NHCH₂(2-pyrimidinyl) 414

INDEX TABLE E-2

Cmpd. R³ position MS No. on ring R³ data 47 5 —C(Me)═NOCH₂CH═CH₂ 375.1448 4,5 4-Me, 5-[—C(Me)═NO(2-pyrimidinyl)] 428.15 49 4,5 4-Me,5-[—C(Me)═NO(5-methoxy-2-pyrimidinyl)] 458.17 50 4,5 4-Me,5-[—C(Me)═NO(4-(CF₃)-2-pyridinyl)] 495.13 51 4,5 4-Me,5-[—C(Me)═NO(4-(CF₃)-2-pyrimidinyl)] 496.18 52 4,5 4-Me,5-[—C(Me)═NO(5-fluoro-2-pyrimidinyl)] 53 4,5 4-Me,5-[—C(Me)═NO(4,6-dimethoxy-2-pyrimidinyl)] 488.10 54 4,5 4-Me,5-[—C(Me)═NO(6-(CF₃)-2-pyridinyl)] 495.13 55 4,5 4-Me, 5-[—C(O)NHCH₂CF₃]418.14 56 4,5 4-Me, 5-[—C(O)NHC(Me)₂CH₂SMe] 438.24 57 4,5 4-Me,5-[—C(O)NHNHC(O)OMe] 409.17 58 4,5 4-Me, 5-[—C(O)NHCH₂CH₂SMe] 410.19 594,5 4-Me, 5-[—CH═NOCH₂CH═CH₂] 376.19 60 5 —C(O)NHCH₂(2-pyrimidinyl)414.2 61 5 —C(O)NH(cyclopropyl) 62 5 —C(O)NHC(Me)₂CH₂SMe 63 5—C(O)NHC(Me)₂CH₂S(O)Me 64 4 —C(O)NH(4-tetrahydropyranyl) 406 65 4—C(O)NHCH₂CH(OMe)₂ 410 66 4 —C(O)NHCH₂(2-pyrimidinyl) 414 67 4—C(O)NHC(Me)₂C(O)OMe 422 68 4 —C(O)NHC(Me)₂C(O)NHMe 421 69 4—C(O)NHC(Me)₂C(O)NMe₂ 435 70 4,5 4-Me, 5-[—C(O)NHC(Me)₂CN] 71 4,5 4-Me,5-[—C(O)NHC(Me)₂C(O)NMe₂] 72 4,5 4-Me, 5-[—C(O)N(Me)C(Me)₂CN] 73 4,54-Me, 5-[—C(O)NHC(Me)₂C(O)NHMe] 74 4,5 4-Me, 5-[—C(O)NHC(Me)₂C(O)NHEt]75 4,5 4-Me, 5-[—C(O)NHCH(Me)CH₂S(O)Me] 440.15

INDEX TABLE E-3

Cmpd. R³ position MS No. on ring R³ data 78 4 —C(O)NHCH₂(2-pyrimidinyl)414.1 79 4 —C(O)NH(cyclopropyl)

INDEX TABLE F

Cmpd. MS No. R³ data  99 —C(O)NHC(—CH₂CH₂—)C(O)OMe 405 105—C(O)NHC(Me)₂C(O)OMe 407.24 112 —C(O)NHC(Me)₂C(O)NH(isopropyl) 433.90114 —C(O)NHC(Me)₂C(O)NHEt 406.06 115 —C(O)NHCH₂(2-pyrimidinyl) 399 118—C(O)NH(4-morpholino) 391 122 —C(O)NHC(Me)₂CH₂SMe 409 124—C(O)NHC(Me)₂C(O)NHEt 420 125 —C(O)NHC(Me)₂CH₂S(O)Me 425 126—C(O)NHC(Me)₂CH₂SO₂Me 440.90 127 —C(O)NHC(Me)₂CN 374 130 —C(O)NHCH₂CN344 (M-1) 134 —C(O)NHC(Me)₂CH₂CH₂SMe 381 138 —C(O)NHC(—CH₂CH₂—)C(O)NH₂390 139 —C(O)NHC(Me)₂C(O)NMe₂ 420 140 —C(O)NHC(Me)₂C(O)NH₂ 392 141—C(O)NHCH₂CH₂S(O)Me 397 142 —C(O)NHCH₂CH₂SO₂Me 413 143—C(O)NHCH(Me)CH₂SMe 395 148 —C(O)NHCH(Me)CH₂S(O)Me 411 149—C(O)NHCH(Me)CH₂SO₂Me 427 167 —C(O)NHC(—CH₂CH₂—)C(O)NH(isopropyl) 432168 —C(O)NHC(Me)(Et)C(O)NH(cyclopropyl) 446 169—C(O)NHC(Me)₂C(O)NH(cyclopropyl) 432 170 —C(O)NHC(—CH₂CH₂—)CH₂S(O)Me 423171 —C(O)NHC(—CH₂CH₂—)CH₂SO₂Me 438.90 177 —C(O)NHC(Me)(Et)C(O)NH₂ 406178 —C(O)NHC(—CH₂CH₂—)CH₂SMe 407 180 —C(O)NHC(Me)(Et)C(O)NH(isopropyl)448

INDEX TABLE G

Cmpd. MS No. R³ data 100 —C(O)NH(4-morpholino) 407 109—C(O)NHC(—CH₂CH₂—)C(O)NH(cyclopropyl) 446 110—C(O)NHC(—CH₂CH₂—)C(O)NH(isopropyl) 448 111 —C(O)NHC(—CH₂CH₂—)C(O)NMe₂434 113 —C(O)NHC(—CH₂CH₂—)C(O)NHEt 434 116 —C(O)NHC(—CH₂CH₂—)C(O)NHMe420 117 —C(O)NHC(Me)₂CN 390 119 —C(O)NHC(Me)₂CH₂SMe 424.90 120—C(O)NH(cyclopropyl) 363 121 —C(O)NHCH₂(2-pyrimidinyl) 414.90 123—C(O)NHC(Me)₂CH₂S(O)Me 441 128 —C(O)NHC(Me)₂C(O)OMe 423 129—C(O)NHC(Me)₂CH₂SO₂Me 456.90 131 —C(O)NMeC(Me)₂CN 404.13 132—C(O)NHC(Me)₂C(O)NHMe 422 133 —C(O)NHC(Me)₂C(O)NHEt 436 135—C(O)NHC(Me)₂C(O)NMe₂ 436 136 —C(O)NHC(Me)₂C(O)NH(isopropyl) 450 137—C(O)NHCH(Me)CH₂SMe 411 144 —C(O)NHCH(Me)CH₂SO₂Me 442.90 150—C(O)NHC(—CH₂CH₂—)C(O)NH₂ 406 151 —C(O)NHC(Me)₂C(O)NH(cyclopropyl) 448152 —C(O)NHC(Me)₂C(O)NH₂ 408 153 —C(O)NHCH(Me)CH₂S(O)Me 426.90 172—C(O)NHCH₂CH₂SMe 397 173 —C(O)NHC(—CH₂CH₂—)CH₂SMe 422.90 179—C(O)NHC(Me)(Et)C(O)NH(isopropyl) 464 181—C(O)NHC(Me)(Et)C(O)NH(cyclopropyl) 462 182 —C(O)NHCH₂CH₂S(O)Me 413 183—C(O)NHC(—CH₂CH₂—)CH₂S(O)Me 438.90 184 —C(O)NHC(—CH₂CH₂—)CH₂SO₂Me 454.90

A compound of this invention will generally be used as an invertebratepest control active ingredient in a composition, i.e. formulation, withat least one additional component selected from the group consisting ofsurfactants, solid diluents and liquid diluents, which serves as acarrier. The formulation or composition ingredients are selected to beconsistent with the physical properties of the active ingredient, modeof application and environmental factors such as soil type, moisture andtemperature.

Useful formulations include both liquid and solid compositions. Liquidcompositions include solutions (including emulsifiable concentrates),suspensions, emulsions (including microemulsions, oil in wateremulsions, flowable concentrates and/or suspoemulsions) and the like,which optionally can be thickened into gels. The general types ofaqueous liquid compositions are soluble concentrate, suspensionconcentrate, capsule suspension, concentrated emulsion, microemulsion,oil in water emulsion, flowable concentrate and suspoemulsion. Thegeneral types of nonaqueous liquid compositions are emulsifiableconcentrate, microemulsifiable concentrate, dispersible concentrate andoil dispersion.

The general types of solid compositions are dusts, powders, granules,pellets, prills, pastilles, tablets, filled films (including seedcoatings) and the like, which can be water-dispersible (“wettable”) orwater-soluble. Films and coatings formed from film-forming solutions orflowable suspensions are particularly useful for seed treatment. Activeingredient can be (micro)encapsulated and further formed into asuspension or solid formulation; alternatively the entire formulation ofactive ingredient can be encapsulated (or “overcoated”). Encapsulationcan control or delay release of the active ingredient. An emulsifiablegranule combines the advantages of both an emulsifiable concentrateformulation and a dry granular formulation. High-strength compositionsare primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable mediumbefore spraying. Such liquid and solid formulations are formulated to bereadily diluted in the spray medium, usually water, but occasionallyanother suitable medium like an aromatic or paraffinic hydrocarbon orvegetable oil. Spray volumes can range from about one to severalthousand liters per hectare, but more typically are in the range fromabout ten to several hundred liters per hectare. Sprayable formulationscan be tank mixed with water or another suitable medium for foliartreatment by aerial or ground application, or for application to thegrowing medium of the plant. Liquid and dry formulations can be metereddirectly into drip irrigation systems or metered into the furrow duringplanting. Liquid and solid formulations can be applied onto seeds ofcrops and other desirable vegetation as seed treatments before plantingto protect developing roots and other subterranean plant parts and/orfoliage through systemic uptake.

The formulations will typically contain effective amounts of activeingredient, diluent and surfactant within the following approximateranges which add up to 100 percent by weight.

Weight Percent Active Ingredient Diluent Surfactant Water-Dispersibleand Water- 0.001-90      0-99.999  0-15 soluble Granules, Tablets andPowders Oil Dispersions, Suspensions,  1-50 40-99  0-50 Emulsions,Solutions (including Emulsifiable Concentrates) Dusts  1-25 70-99 0-5Granules and Pellets 0.001-99      5-99.999  0-15 High StrengthCompositions 90-99  0-10 0-2

Solid diluents include, for example, clays such as bentonite,montmorillonite, attapulgite and kaolin, gypsum, cellulose, titaniumdioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose),silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodiumcarbonate and bicarbonate, and sodium sulfate. Typical solid diluentsare described in Watkins et al., Handbook of Insecticide Dust Diluentsand Carriers, 2nd Ed., Dorland Books, Caldwell, N.J.

Liquid diluents include, for example, water, N,N-dimethylalkanamides(e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide,N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates(e.g., triethylphosphate), ethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol, polypropylene glycol, propylenecarbonate, butylene carbonate, paraffins (e.g., white mineral oils,normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes,glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons,dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones suchas cyclohexanone, 2-heptanone, isophorone and4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexylacetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetateand isobornyl acetate, other esters such as alkylated lactate esters,dibasic esters alkyl and aryl benzoates, γ-butyrolactone, and alcohols,which can be linear, branched, saturated or unsaturated, such asmethanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutylalcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecylalcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecylalcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol,diacetone alcohol, cresol and benzyl alcohol. Liquid diluents alsoinclude glycerol esters of saturated and unsaturated fatty acids(typically C₆-C₂₂), such as plant seed and fruit oils (e.g., oils ofolive, castor, linseed, sesame, corn (maize), peanut, sunflower,grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palmkernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, codliver oil, fish oil), and mixtures thereof. Liquid diluents also includealkylated fatty acids (e.g., methylated, ethylated, butylated) whereinthe fatty acids may be obtained by hydrolysis of glycerol esters fromplant and animal sources, and can be purified by distillation. Typicalliquid diluents are described in Marsden, Solvents Guide, 2nd Ed.,Interscience, New York, 1950.

The solid and liquid compositions of the present invention often includeone or more surfactants. When added to a liquid, surfactants (also knownas “surface-active agents”) generally modify, most often reduce, thesurface tension of the liquid. Depending on the nature of thehydrophilic and lipophilic groups in a surfactant molecule, surfactantscan be useful as wetting agents, dispersants, emulsifiers or defoamingagents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionicsurfactants useful for the present compositions include, but are notlimited to: alcohol alkoxylates such as alcohol alkoxylates based onnatural and synthetic alcohols (which may be branched or linear) andprepared from the alcohols and ethylene oxide, propylene oxide, butyleneoxide or mixtures thereof; amine ethoxylates, alkanolamides andethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylatedsoybean, castor and rapeseed oils; alkylphenol alkoxylates such asoctylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenolethoxylates and dodecyl phenol ethoxylates (prepared from the phenolsand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); block polymers prepared from ethylene oxide or propylene oxideand reverse block polymers where the terminal blocks are prepared frompropylene oxide; ethoxylated fatty acids; ethoxylated fatty esters andoils; ethoxylated methyl esters; ethoxylated tristyrylphenol (includingthose prepared from ethylene oxide, propylene oxide, butylene oxide ormixtures thereof); fatty acid esters, glycerol esters, lanolin-basedderivatives, polyethoxylate esters such as polyethoxylated sorbitanfatty acid esters, polyethoxylated sorbitol fatty acid esters andpolyethoxylated glycerol fatty acid esters; other sorbitan derivativessuch as sorbitan esters; polymeric surfactants such as randomcopolymers, block copolymers, alkyd peg (polyethylene glycol) resins,graft or comb polymers and star polymers; polyethylene glycols (pegs);polyethylene glycol fatty acid esters; silicone-based surfactants; andsugar-derivatives such as sucrose esters, alkyl polyglycosides and alkylpolysaccharides.

Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; carboxylated alcohol or alkylphenolethoxylates; diphenyl sulfonate derivatives; lignin and ligninderivatives such as lignosulfonates; maleic or succinic acids or theiranhydrides; olefin sulfonates; phosphate esters such as phosphate estersof alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates andphosphate esters of styryl phenol ethoxylates; protein-basedsurfactants; sarcosine derivatives; styryl phenol ether sulfate;sulfates and sulfonates of oils and fatty acids; sulfates and sulfonatesof ethoxylated alkylphenols; sulfates of alcohols; sulfates ofethoxylated alcohols; sulfonates of amines and amides such asN,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, anddodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes;sulfonates of naphthalene and alkyl naphthalene; sulfonates offractionated petroleum; sulfosuccinamates; and sulfosuccinates and theirderivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides andethoxylated amides; amines such as N-alkyl propanediamines,tripropylenetriamines and dipropylenetetramines, and ethoxylated amines,ethoxylated diamines and propoxylated amines (prepared from the aminesand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); amine salts such as amine acetates and diamine salts;quaternary ammonium salts such as quaternary salts, ethoxylatedquaternary salts and diquaternary salts; and amine oxides such asalkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic andanionic surfactants or mixtures of nonionic and cationic surfactants.Nonionic, anionic and cationic surfactants and their recommended usesare disclosed in a variety of published references includingMcCutcheon's Emulsifiers and Detergents, annual American andInternational Editions published by McCutcheon's Division, TheManufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopediaof Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; andA. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition,John Wiley and Sons, New York, 1987.

Compositions of this invention may also contain formulation auxiliariesand additives, known to those skilled in the art as formulation aids(some of which may be considered to also function as solid diluents,liquid diluents or surfactants). Such formulation auxiliaries andadditives may control: pH (buffers), foaming during processing(antifoams such polyorganosiloxanes), sedimentation of activeingredients (suspending agents), viscosity (thixotropic thickeners),in-container microbial growth (antimicrobials), product freezing(antifreezes), color (dyes/pigment dispersions), wash-off (film formersor stickers), evaporation (evaporation retardants), and otherformulation attributes. Film formers include, for example, polyvinylacetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinylacetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers andwaxes. Examples of formulation auxiliaries and additives include thoselisted in McCutcheon's Volume 2: Functional Materials, annualInternational and North American editions published by McCutcheon'sDivision, The Manufacturing Confectioner Publishing Co.; and PCTPublication WO 03/024222.

The compound of Formula 1 and any other active ingredients are typicallyincorporated into the present compositions by dissolving the activeingredient in a solvent or by grinding in a liquid or dry diluent.Solutions, including emulsifiable concentrates, can be prepared bysimply mixing the ingredients. If the solvent of a liquid compositionintended for use as an emulsifiable concentrate is water-immiscible, anemulsifier is typically added to emulsify the active-containing solventupon dilution with water. Active ingredient slurries, with particlediameters of up to 2,000 Lm can be wet milled using media mills toobtain particles with average diameters below 3 am. Aqueous slurries canbe made into finished suspension concentrates (see, for example, U.S.Pat. No. 3,060,084) or further processed by spray drying to formwater-dispersible granules. Dry formulations usually require dry millingprocesses, which produce average particle diameters in the 2 to 10 amrange. Dusts and powders can be prepared by blending and usuallygrinding (such as with a hammer mill or fluid-energy mill). Granules andpellets can be prepared by spraying the active material upon preformedgranular carriers or by agglomeration techniques. See Browning,“Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry'sChemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963,pages 8-57 and following, and WO 91/13546. Pellets can be prepared asdescribed in U.S. Pat. No. 4,172,714. Water-dispersible andwater-soluble granules can be prepared as taught in U.S. Pat. Nos.4,144,050, 3,920,442 and DE 3,246,493. Tablets can be prepared as taughtin U.S. Pat. Nos. 5,180,587, 5,232,701 and 5,208,030. Films can beprepared as taught in GB 2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see T. S.Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture”in Pesticide Chemistry and Bioscience, The Food-Environment Challenge,T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th InternationalCongress on Pesticide Chemistry, The Royal Society of Chemistry,Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6,line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No.3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12,15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 andExamples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons,Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8thEd., Blackwell Scientific Publications, Oxford, 1989; and Developmentsin formulation technology, PJB Publications, Richmond, U K, 2000.

In the following Examples, all formulations are prepared in conventionalways. Compound numbers refer to compounds in Index Tables A-G. Withoutfurther elaboration, it is believed that one skilled in the art usingthe preceding description can utilize the present invention to itsfullest extent. The following Examples are, therefore, to be construedas merely illustrative, and not limiting of the disclosure in any waywhatsoever. Percentages are by weight except where otherwise indicated.

Example A High Strength Concentrate

Compound 11 98.5% silica aerogel  0.5% synthetic amorphous fine silica 1.0%

Example B Wettable Powder

Compound 12 65.0% dodecylphenol polyethylene glycol ether  2.0% sodiumligninsulfonate  4.0% sodium silicoaluminate  6.0% montmorillonite(calcined) 23.0%

Example C Granule

Compound 20 10.0% attapulgite granules (low volatile matter, 90.0%0.71/0.30 mm; U.S.S. No. 25-50 sieves)

Example D Extruded Pellet

Compound 24 25.0% anhydrous sodium sulfate 10.0% crude calciumligninsulfonate  5.0% sodium alkylnaphthalenesulfonate  1.0%calcium/magnesium bentonite 59.0%

Example E Emulsifiable Concentrate

Compound 25 10.0% polyoxyethylene sorbitol hexoleate 20.0% C₆-C₁₀ fattyacid methyl ester 70.0%

Example F Microemulsion

Compound 26  5.0% polyvinylpyrrolidone-vinyl acetate copolymer 30.0%alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0%

Example G Seed Treatment

Compound 30 20.00% polyvinylpyrrolidone-vinyl acetate copolymer  5.00%montan acid wax  5.00% calcium ligninsulfonate  1.00%polyoxyethylene/polyoxypropylene block copolymers  1.00% stearyl alcohol(POE 20)  2.00% polyorganosilane  0.20% colorant red dye  0.05% water65.75%

Example H Fertilizer Stick

Compound 31  2.5% pyrrolidone-styrene copolymer  4.8% tristyrylphenyl16-ethoxylate  2.3% talc  0.8% corn starch  5.0% slow-release fertilizer36.0% kaolin 38.0% water 10.6%

Example I Suspension Concentrate

compound 47   35% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer  1.0% styrene acrylicpolymer  1.0% xanthan gum  0.1% propylene glycol  5.0% silicone baseddefoamer  0.1% 1,2-benzisothiazolin-3-one  0.1% water 53.7%

Example J Emulsion in Water

compound 56 10.0% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer  1.0% styrene acrylicpolymer  1.0% xanthan gum  0.1% propylene glycol  5.0% silicone baseddefoamer  0.1% 1,2-benzisothiazolin-3-one  0.1% aromatic petroleum basedhydrocarbon 20.0 water 58.7%

Example K Oil Dispersion

compound 59   25% polyoxyethylene sorbitol hexaoleate   15% organicallymodified bentonite clay  2.5% fatty acid methyl ester 57.5%

Example L Suspoemulsion

compound 62 10.0% imidacloprid  5.0% butyl polyoxyethylene/polypropyleneblock copolymer  4.0% stearic acid/polyethylene glycol copolymer  1.0%styrene acrylic polymer  1.0% xanthan gum  0.1% propylene glycol  5.0%silicone based defoamer  0.1% 1,2-benzisothiazolin-3-one  0.1% aromaticpetroleum based hydrocarbon 20.0% water 53.7%

Compounds of this invention exhibit activity against a wide spectrum ofinvertebrate pests. These pests include invertebrates inhabiting avariety of environments such as, for example, plant foliage, roots,soil, harvested crops or other foodstuffs, building structures or animalinteguments. These pests include, for example, invertebrates feeding onfoliage (including leaves, stems, flowers and fruits), seeds, wood,textile fibers or animal blood or tissues, and thereby causing injury ordamage to, for example, growing or stored agronomic crops, forests,greenhouse crops, ornamentals, nursery crops, stored foodstuffs or fiberproducts, or houses or other structures or their contents, or beingharmful to animal health or public health. Those skilled in the art willappreciate that not all compounds are equally effective against allgrowth stages of all pests.

These present compounds and compositions are thus useful agronomicallyfor protecting field crops from phytophagous invertebrate pests, andalso nonagronomically for protecting other horticultural crops andplants from phytophagous invertebrate pests. This utility includesprotecting crops and other plants (i.e. both agronomic and nonagronomic)that contain genetic material introduced by genetic engineering (i.e.transgenic) or modified by mutagenesis to provide advantageous traits.Examples of such traits include tolerance to herbicides, resistance tophytophagous pests (e.g., insects, mites, aphids, spiders, nematodes,snails, plant-pathogenic fungi, bacteria and viruses), improved plantgrowth, increased tolerance of adverse growing conditions such as highor low temperatures, low or high soil moisture, and high salinity,increased flowering or fruiting, greater harvest yields, more rapidmaturation, higher quality and/or nutritional value of the harvestedproduct, or improved storage or process properties of the harvestedproducts. Transgenic plants can be modified to express multiple traits.Examples of plants containing traits provided by genetic engineering ormutagenesis include varieties of corn, cotton, soybean and potatoexpressing an insecticidal Bacillus thuringiensis toxin such as YIELDGARD®, KNOCKOUT®, STARLINK®, BOLLGARD®, NuCOTN® and NEWLEAF®, INVICTARR2 PRO™, and herbicide-tolerant varieties of corn, cotton, soybean andrapeseed such as ROUNDUP READY®, LIBERTY LINK®, IMI®, STS® andCLEARFIELD®, as well as crops expressing N-acetyltransferase (GAT) toprovide resistance to glyphosate herbicide, or crops containing the HRAgene providing resistance to herbicides inhibiting acetolactate synthase(ALS). The present compounds and compositions may interactsynergistically with traits introduced by genetic engineering ormodified by mutagenesis, thus enhancing phenotypic expression oreffectiveness of the traits or increasing the invertebrate pest controleffectiveness of the present compounds and compositions. In particular,the present compounds and compositions may interact synergistically withthe phenotypic expression of proteins or other natural products toxic toinvertebrate pests to provide greater-than-additive control of thesepests.

Compositions of this invention can also optionally comprise plantnutrients, e.g., a fertilizer composition comprising at least one plantnutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium,magnesium, iron, copper, boron, manganese, zinc, and molybdenum. Of noteare compositions comprising at least one fertilizer compositioncomprising at least one plant nutrient selected from nitrogen,phosphorus, potassium, sulfur, calcium and magnesium. Compositions ofthe present invention which further comprise at least one plant nutrientcan be in the form of liquids or solids. Of note are solid formulationsin the form of granules, small sticks or tablets. Solid formulationscomprising a fertilizer composition can be prepared by mixing thecompound or composition of the present invention with the fertilizercomposition together with formulating ingredients and then preparing theformulation by methods such as granulation or extrusion. Alternativelysolid formulations can be prepared by spraying a solution or suspensionof a compound or composition of the present invention in a volatilesolvent onto a previous prepared fertilizer composition in the form ofdimensionally stable mixtures, e.g., granules, small sticks or tablets,and then evaporating the solvent.

Nonagronomic uses refer to invertebrate pest control in the areas otherthan fields of crop plants. Nonagronomic uses of the present compoundsand compositions include control of invertebrate pests in stored grains,beans and other foodstuffs, and in textiles such as clothing andcarpets. Nonagronomic uses of the present compounds and compositionsalso include invertebrate pest control in ornamental plants, forests, inyards, along roadsides and railroad rights of way, and on turf such aslawns, golf courses and pastures. Nonagronomic uses of the presentcompounds and compositions also include invertebrate pest control inhouses and other buildings which may be occupied by humans and/orcompanion, farm, ranch, zoo or other animals. Nonagronomic uses of thepresent compounds and compositions also include the control of pestssuch as termites that can damage wood or other structural materials usedin buildings.

Nonagronomic uses of the present compounds and compositions also includeprotecting human and animal health by controlling invertebrate peststhat are parasitic or transmit infectious diseases. The controlling ofanimal parasites includes controlling external parasites that areparasitic to the surface of the body of the host animal (e.g.,shoulders, armpits, abdomen, inner part of the thighs) and internalparasites that are parasitic to the inside of the body of the hostanimal (e.g., stomach, intestine, lung, veins, under the skin, lymphatictissue). External parasitic or disease transmitting pests include, forexample, chiggers, ticks, lice, mosquitoes, flies, mites and fleas.Internal parasites include heartworms, hookworms and helminths.Compounds and compositions of the present invention are suitable forsystemic and/or non-systemic control of infestation or infection byparasites on animals. Compounds and compositions of the presentinvention are particularly suitable for combating external parasitic ordisease transmitting pests. Compounds and compositions of the presentinvention are suitable for combating parasites that infest agriculturalworking animals, such as cattle, sheep, goats, horses, pigs, donkeys,camels, buffalos, rabbits, hens, turkeys, ducks, geese and bees; petanimals and domestic animals such as dogs, cats, pet birds and aquariumfish; as well as so-called experimental animals, such as hamsters,guinea pigs, rats and mice. By combating these parasites, fatalities andperformance reduction (in terms of meat, milk, wool, skins, eggs, honey,etc.) are reduced, so that applying a composition comprising a compoundof the present invention allows more economic and simple husbandry ofanimals.

Examples of agronomic or nonagronomic invertebrate pests include eggs,larvae and adults of the order Lepidoptera, such as armyworms, cutworms,loopers, and heliothines in the family Noctuidae (e.g., pink stem borer(Sesamia inferens Walker), corn stalk borer (Sesamia nonagrioidesLefebvre), southern armyworm (Spodoptera eridania Cramer), fall armyworm(Spodoptera frugiperda J. E. Smith), beet armyworm (Spodoptera exiguaHübner), cotton leafworm (Spodoptera littoralis Boisduval),yellowstriped armyworm (Spodoptera ornithogalli Guenee), black cutworm(Agrotis ipsilon Hufnagel), velvetbean caterpillar (Anticarsiagemmatalis Hübner), green fruitworm (Lithophane antennata Walker),cabbage armyworm (Barathra brassicae Linnaeus), soybean looper(Pseudoplusia includens Walker), cabbage looper (Trichoplusia niHübner), tobacco budworm (Heliothis virescens Fabricius)); borers,casebearers, webworms, coneworms, cabbageworms and skeletonizers fromthe family Pyralidae (e.g., European corn borer (Ostrinia nubilalisHübner), navel orangeworm (Amyelois transitella Walker), corn rootwebworm (Crambus caliginosellus Clemens), sod webworms (Pyralidae:Crambinae) such as sod worm (Herpetogramma licarsisalis Walker),sugarcane stem borer (Chilo infuscatellus Snellen), tomato small borer(Neoleucinodes elegantalis Guenee), green leafroller (Cnaphalocrocismedinalis), grape leaffolder (Desmia funeralis Hübner), melon worm(Diaphania nitidalis Stoll), cabbage center grub (Helluala hydralisGuenee), yellow stem borer (Scirpophaga incertulas Walker), early shootborer (Scirpophaga infuscatellus Snellen), white stem borer (Scirpophagainnotata Walker), top shoot borer (Scirpophaga nivella Fabricius),dark-headed rice borer (Chilo polychrysus Meyrick), striped riceborer(Chilo suppressalis Walker), cabbage cluster caterpillar (Crocidolomiabinotalis English)); leafrollers, budworms, seed worms, and fruit wormsin the family Tortricidae (e.g., codling moth (Cydia pomonellaLinnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruitmoth (Grapholita molesta Busck), citrus false codling moth(Cryptophlebia leucotreta Meyrick), citrus borer (Ecdytolopha aurantianaLima), redbanded leafroller (Argyrotaenia velutinana Walker),obliquebanded leafroller (Choristoneura rosaceana Harris), light brownapple moth (Epiphyas postvittana Walker), European grape berry moth(Eupoecilia ambiguella Hübner), apple bud moth (Pandemis pyrusanaKearfott), omnivorous leafroller (Platynota stultana Walsingham), barredfruit-tree tortrix (Pandemis cerasana Hübner), apple brown tortrix(Pandemis heparana Denis & Schiffermuller)); and many other economicallyimportant lepidoptera (e.g., diamondback moth (Plutella xylostellaLinnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth(Lymantria dispar Linnaeus), peach fruit borer (Carposina niponensisWalsingham), peach twig borer (Anarsia lineatella Zeller), potatotuberworm (Phthorimaea operculella Zeller), spotted teniform leafminer(Lithocolletis blancardella Fabricius), Asiatic apple leafminer(Lithocolletis ringoniella Matsumura), rice leaffolder (Lerodea eufalaEdwards), apple leafminer (Leucoptera scitella Zeller)); eggs, nymphsand adults of the order Blattodea including cockroaches from thefamilies Blattellidae and Blattidae (e.g., oriental cockroach (Blattaorientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo),German cockroach (Blattella germanica Linnaeus), brownbanded cockroach(Supella longipalpa Fabricius), American cockroach (Periplanetaamericana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister),Madeira cockroach (Leucophaea maderae Fabricius)), smoky brown cockroach(Periplaneta fuliginosa Service), Australian Cockroach (Periplanetaaustralasiae Fabr.), lobster cockroach (Nauphoeta cinerea Olivier) andsmooth cockroach (Symploce pallens Stephens)); eggs, foliar feeding,fruit feeding, root feeding, seed feeding and vesicular tissue feedinglarvae and adults of the order Coleoptera including weevils from thefamilies Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil(Anthonomus grandis Boheman), rice water weevil (Lissorhoptrusoryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus),rice weevil (Sitophilus oryzae Linnaeus)), annual bluegrass weevil(Listronotus maculicollis Dietz), bluegrass billbug (Sphenophorusparvulus Gyllenhal), hunting billbug (Sphenophorus venatus vestitus),Denver billbug (Sphenophorus cicatristriatus Fahraeus)); flea beetles,cucumber beetles, rootworms, leaf beetles, potato beetles, andleafminers in the family Chrysomelidae (e.g., Colorado potato beetle(Leptinotarsa decemlineata Say), western corn rootworm (Diabroticavirgifera virgifera LeConte)); chafers and other beetles from the familyScarabaeidae (e.g., Japanese beetle (Popillia japonica Newman), orientalbeetle (Anomala orientalis Waterhouse, Exomala orientalis (Waterhouse)Baraud), northern masked chafer (Cyclocephala borealis Arrow), southernmasked chafer (Cyclocephala immaculata Olivier or C. lurida Bland), dungbeetle and white grub (Aphodius spp.), black turfgrass ataenius(Ataenius spretulus Haldeman), green June beetle (Cotinis nitidaLinnaeus), Asiatic garden beetle (Maladera castanea Arrow), May/Junebeetles (Phyllophaga spp.) and European chafer (Rhizotrogus majalisRazoumowsky)); carpet beetles from the family Dermestidae; wirewormsfrom the family Elateridae; bark beetles from the family Scolytidae andflour beetles from the family Tenebrionidae.

In addition, agronomic and nonagronomic pests include: eggs, adults andlarvae of the order Dermaptera including earwigs from the familyForficulidae (e.g., European earwig (Forficula auricularia Linnaeus),black earwig (Chelisoches morio Fabricius)); eggs, immatures, adults andnymphs of the orders Hemiptera and Homoptera such as, plant bugs fromthe family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g.Empoasca spp.) from the family Cicadellidae, bed bugs (e.g., Cimexlectularius Linnaeus) from the family Cimicidae, planthoppers from thefamilies Fulgoroidae and Delphacidae, treehoppers from the familyMembracidae, psyllids from the family Psyllidae, whiteflies from thefamily Aleyrodidae, aphids from the family Aphididae, phylloxera fromthe family Phylloxeridae, mealybugs from the family Pseudococcidae,scales from the families Coccidae, Diaspididae and Margarodidae, lacebugs from the family Tingidae, stink bugs from the family Pentatomidae,chinch bugs (e.g., hairy chinch bug (Blissus leucopterus hirtusMontandon) and southern chinch bug (Blissus insularis Barber)) and otherseed bugs from the family Lygaeidae, spittlebugs from the familyCercopidae squash bugs from the family Coreidae, and red bugs and cottonstainers from the family Pyrrhocoridae.

Agronomic and nonagronomic pests also include: eggs, larvae, nymphs andadults of the order Acari (mites) such as spider mites and red mites inthe family Tetranychidae (e.g., European red mite (Panonychus ulmiKoch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite(Tetranychus mcdanieli McGregor)); flat mites in the familyTenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor));rust and bud mites in the family Eriophyidae and other foliar feedingmites and mites important in human and animal health, i.e. dust mites inthe family Epidermoptidae, follicle mites in the family Demodicidae,grain mites in the family Glycyphagidae; ticks in the family Ixodidae,commonly known as hard ticks (e.g., deer tick (Ixodes scapularis Say),Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick(Dermacentor variabilis Say), lone star tick (Amblyomma americanumLinnaeus)) and ticks in the family Argasidae, commonly known as softticks (e.g., relapsing fever tick (Ornithodoros turicata), common fowltick (Argas radiatus)); scab and itch mites in the families Psoroptidae,Pyemotidae, and Sarcoptidae; eggs, adults and immatures of the orderOrthoptera including grasshoppers, locusts and crickets (e.g., migratorygrasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialisThomas), American grasshoppers (e.g., Schistocerca americana Drury),desert locust (Schistocerca gregaria Forskal), migratory locust (Locustamigratoria Linnaeus), bush locust (Zonocerus spp.), house cricket(Acheta domesticus Linnaeus), mole crickets (e.g., tawny mole cricket(Scapteriscus vicinus Scudder) and southern mole cricket (Scapteriscusborellii Giglio-Tos)); eggs, adults and immatures of the order Dipteraincluding leafminers (e.g., Liriomyza spp. such as serpentine vegetableleafminer (Liriomyza sativae Blanchard)), midges, fruit flies(Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots,house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g.,Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (e.g.,Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g.,Chrysomya spp., Phormia spp.), and other muscoid fly pests, horse flies(e.g., Tabanus spp.), bot flies (e.g., Gastrophilus spp., Oestrus spp.),cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.),keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes(e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g.,Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids,and other Nematocera; eggs, adults and immatures of the orderThysanoptera including onion thrips (Thrips tabaci Lindeman), flowerthrips (Frankliniella spp.), and other foliar feeding thrips; insectpests of the order Hymenoptera including ants of the Family Formicidaeincluding the Florida carpenter ant (Camponotus floridanus Buckley), redcarpenter ant (Camponotus ferrugineus Fabricius), black carpenter ant(Camponotus pennsylvanicus De Geer), white-footed ant (Technomyrmexalbipes fr. Smith), big headed ants (Pheidole sp.), ghost ant (Tapinomamelanocephalum Fabricius); Pharaoh ant (Monomorium pharaonis Linnaeus),little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsisgeminata Fabricius), red imported fire ant (Solenopsis invicta Buren),Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechinalongicornis Latreille), pavement ant (Tetramorium caespitum Linnaeus),cornfield ant (Lasius alienus Forster) and odorous house ant (Tapinomasessile Say). Other Hymenoptera including bees (including carpenterbees), hornets, yellow jackets, wasps, and sawflies (Neodiprion spp.;Cephus spp.); insect pests of the order Isoptera including termites inthe Termitidae (e.g., Macrotermes sp., Odontotermes obesus Rambur),Kalotermitidae (e.g., Cryptotermes sp.), and Rhinotermitidae (e.g.,Reticulitermes sp., Coptotermes sp., Heterotermes tenuis Hagen)families, the eastern subterranean termite (Reticulitermes flavipesKollar), western subterranean termite (Reticulitermes hesperus Banks),Formosan subterranean termite (Coptotermes formosanus Shiraki), WestIndian drywood termite (Incisitermes immigrans Snyder), powder posttermite (Cryptotermes brevis Walker), drywood termite (Incisitermessnyderi Light), southeastern subterranean termite (Reticulitermesvirginicus Banks), western drywood termite (Incisitermes minor Hagen),arboreal termites such as Nasutitermes sp. and other termites ofeconomic importance; insect pests of the order Thysanura such assilverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobiadomestica Packard); insect pests of the order Mallophaga and includingthe head louse (Pediculus humanus capitis De Geer), body louse(Pediculus humanus Linnaeus), chicken body louse (Menacanthus stramineusNitszch), dog biting louse (Trichodectes canis De Geer), fluff louse(Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank),short-nosed cattle louse (Haematopinus eurysternus Nitzsch), long-nosedcattle louse (Linognathus vituli Linnaeus) and other sucking and chewingparasitic lice that attack man and animals; insect pests of the orderSiphonoptera including the oriental rat flea (Xenopsylla cheopisRothschild), cat flea (Ctenocephalides felis Bouche), dog flea(Ctenocephalides canis Curtis), hen flea (Ceratophyllus gallinaeSchrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea(Pulex irritans Linnaeus) and other fleas afflicting mammals and birds.Additional arthropod pests covered include: spiders in the order Araneaesuch as the brown recluse spider (Loxosceles reclusa Gertsch & Mulaik)and the black widow spider (Latrodectus mactans Fabricius), andcentipedes in the order Scutigeromorpha such as the house centipede(Scutigera coleoptrata Linnaeus).

Examples of invertebrate pests of stored grain include larger grainborer (Prostephanus truncatus), lesser grain borer (Rhyzoperthadominica), rice weevil (Stiophilus oryzae), maize weevil (Stiophiluszeamais), cowpea weevil (Callosobruchus maculatus), red flour beetle(Tribolium castaneum), granary weevil (Stiophilus granarius), Indianmeal moth (Plodia interpunctella), Mediterranean flour beetle (Ephestiakuhniella) and flat or rusty grain beetle (Cryptolestis ferrugineus).

Compounds of the present invention may have activity on members of theClasses Nematoda, Cestoda, Trematoda, and Acanthocephala includingeconomically important members of the orders Strongylida, Ascaridida,Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited toeconomically important agricultural pests (i.e. root knot nematodes inthe genus Meloidogyne, lesion nematodes in the genus Pratylenchus,stubby root nematodes in the genus Trichodorus, etc.) and animal andhuman health pests (i.e. all economically important flukes, tapeworms,and roundworms, such as Strongylus vulgaris in horses, Toxocara canis indogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs,Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus inruminants, etc.).

Compounds of the invention may have activity against pests in the orderLepidoptera (e.g., Alabama argillacea Hübner (cotton leaf worm), Archipsargyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus(European leaf roller) and other Archips species, Chilo suppressalisWalker (rice stem borer), Cnaphalocrosis medinalis Guenee (rice leafroller), Crambus caliginosellus Clemens (corn root webworm), Crambusteterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus(codling moth), Earias insulana Boisduval (spiny bollworm), Eariasvittella Fabricius (spotted bollworm), Helicoverpa armigera Hübner(American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothisvirescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker(sod webworm), Lobesia botrana Denis & Schiffermuller (grape berrymoth), Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistiscitrella Stainton (citrus leafminer), Pieris brassicae Linnaeus (largewhite butterfly), Pieris rapae Linnaeus (small white butterfly),Plutella xylostella Linnaeus (diamondback moth), Spodoptera exiguaHübner (beet armyworm), Spodoptera litura Fabricius (tobacco cutworm,cluster caterpillar), Spodoptera frugiperda J. E. Smith (fall armyworm),Trichoplusia ni Hübner (cabbage looper) and Tuta absoluta Meyrick(tomato leafminer)).

Compounds of the invention have significant activity on members from theorder Homoptera including: Acyrthosiphon pisum Harris (pea aphid), Aphiscraccivora Koch (cowpea aphid), Aphisfabae Scopoli (black bean aphid),Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer(apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solaniKaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell(strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheataphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosomalanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy(mealy plum aphid), Lipaphis erysimi Kaltenbach (turnip aphid),Metopolophium dirrhodum Walker (cereal aphid), Macrosiphum euphorbiaeThomas (potato aphid), Myzus persicae Sulzer (peach-potato aphid, greenpeach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigusspp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (cornleaf aphid), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid),Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius(English grain aphid), Therioaphis maculata Buckton (spotted alfalfaaphid), Toxoptera aurantii Boyer de Fonscolombe (black citrus aphid),and Toxoptera citricida Kirkaldy (brown citrus aphid); Adelges spp.(adelgids); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisiatabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisiaargentifolii Bellows & Perring (silverleaf whitefly), Dialeurodes citriAshmead (citrus whitefly) and Trialeurodes vaporariorum Westwood(greenhouse whitefly); Empoasca fabae Harris (potato leafhopper),Laodelphax striatellus Fallen (smaller brown planthopper), Macrolestesquadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler(green leafhopper), Nephotettix nigropictus Stål (rice leafhopper),Nilaparvata lugens Stål (brown planthopper), Peregrinus maidis Ashmead(corn planthopper), Sogatella furcifera Horvath (white-backedplanthopper), Sogatodes orizicola Muir (rice delphacid), Typhlocybapomaria McAtee white apple leafhopper, Erythroneoura spp. (grapeleafhoppers); Magicidada septendecim Linnaeus (periodical cicada);Icerya purchasi Maskell (cottony cushion scale), Quadraspidiotusperniciosus Comstock (San Jose scale); Planococcus citri Risso (citrusmealybug); Pseudococcus spp. (other mealybug complex); Cacopsyllapyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmonpsylla).

Compounds of this invention also have activity on members from the orderHemiptera including: Acrosternum hilare Say (green stink bug), Anasatristis De Geer (squash bug), Blissus leucopterus leucopterus Say(chinch bug), Cimex lectularius Linnaeus (bed bug) Corythuca gossypiiFabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug),Dysdercus suturellus Herrich-Schaffer (cotton stainer), Euchistus servusSay (brown stink bug), Euchistus variolarius Palisot de Beauvois(one-spotted stink bug), Graptosthetus spp. (complex of seed bugs),Halymorpha halys Stål (brown marmorated stink bug), Leptoglossuscorculus Say (leaf-footed pine seed bug), Lygus lineolaris Palisot deBeauvois (tarnished plant bug), Nezara viridula Linnaeus (southern greenstink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltusfasciatus Dallas (large milkweed bug), Pseudatomoscelis seriatus Reuter(cotton fleahopper). Other insect orders controlled by compounds of theinvention include Thysanoptera (e.g., Frankliniella occidentalisPergande (western flower thrips), Scirthothrips citri Moulton (citrusthrips), Sericothrips variabilis Beach (soybean thrips), and Thripstabaci Lindeman (onion thrips); and the order Coleoptera (e.g.,Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachnavarivestis Mulsant (Mexican bean beetle) and wireworms of the generaAgriotes, Athous or Limonius).

Note that some contemporary classification systems place Homoptera as asuborder within the order Hemiptera.

Of note is use of compounds of this invention for controlling westernflower thrips (Frankliniella occidentalis). Of note is use of compoundsof this invention for controlling potato leafhopper (Empoasca fabae). Ofnote is use of compounds of this invention for controlling cotton melonaphid (Aphis gossypii). Of note is use of compounds of this inventionfor controlling green peach aphid (Myzus persicae). Of note is use ofcompounds of this invention for controlling sweetpotato whitefly(Bemisia tabaci).

Compounds of the present invention may also be useful for increasingvigor of a crop plant. This method comprises contacting the crop plant(e.g., foliage, flowers, fruit or roots) or the seed from which the cropplant is grown with a compound of Formula 1 in amount sufficient toachieve the desired plant vigor effect (i.e. biologically effectiveamount). Typically the compound of Formula 1 is applied in a formulatedcomposition. Although the compound of Formula 1 is often applieddirectly to the crop plant or its seed, it can also be applied to thelocus of the crop plant, i.e. the environment of the crop plant,particularly the portion of the environment in close enough proximity toallow the compound of Formula 1 to migrate to the crop plant. The locusrelevant to this method most commonly comprises the growth medium (i.e.medium providing nutrients to the plant), typically soil in which theplant is grown. Treatment of a crop plant to increase vigor of the cropplant thus comprises contacting the crop plant, the seed from which thecrop plant is grown or the locus of the crop plant with a biologicallyeffective amount of a compound of Formula 1.

Increased crop vigor can result in one or more of the following observedeffects: (a) optimal crop establishment as demonstrated by excellentseed germination, crop emergence and crop stand; (b) enhanced cropgrowth as demonstrated by rapid and robust leaf growth (e.g., measuredby leaf area index), plant height, number of tillers (e.g., for rice),root mass and overall dry weight of vegetative mass of the crop; (c)improved crop yields, as demonstrated by time to flowering, duration offlowering, number of flowers, total biomass accumulation (i.e. yieldquantity) and/or fruit or grain grade marketability of produce (i.e.yield quality); (d) enhanced ability of the crop to withstand or preventplant disease infections and arthropod, nematode or mollusk pestinfestations; and (e) increased ability of the crop to withstandenvironmental stresses such as exposure to thermal extremes, suboptimalmoisture or phytotoxic chemicals.

The compounds of the present invention may increase the vigor of treatedplants compared to untreated plants by killing or otherwise preventingfeeding of phytophagous invertebrate pests in the environment of theplants. In the absence of such control of phytophagous invertebratepests, the pests reduce plant vigor by consuming plant tissues or sap,or transmitting plant pathogens such as viruses. Even in the absence ofphytophagous invertebrate pests, the compounds of the invention mayincrease plant vigor by modifying metabolism of plants. Generally, thevigor of a crop plant will be most significantly increased by treatingthe plant with a compound of the invention if the plant is grown in anonideal environment, i.e. an environment comprising one or more aspectsadverse to the plant achieving the full genetic potential it wouldexhibit in an ideal environment.

Of note is a method for increasing vigor of a crop plant wherein thecrop plant is grown in an environment comprising phytophagousinvertebrate pests. Also of note is a method for increasing vigor of acrop plant wherein the crop plant is grown in an environment notcomprising phytophagous invertebrate pests. Also of note is a method forincreasing vigor of a crop plant wherein the crop plant is grown in anenvironment comprising an amount of moisture less than ideal forsupporting growth of the crop plant. Of note is a method for increasingvigor of a crop plant wherein the crop is rice. Also of note is a methodfor increasing vigor of a crop plant wherein the crop is maize (corn).Also of note is a method for increasing vigor of a crop plant whereinthe crop is soybean.

Compounds of this invention can also be mixed with one or more otherbiologically active compounds or agents including insecticides,fungicides, nematocides, bactericides, acaricides, herbicides, herbicidesafeners, growth regulators such as insect molting inhibitors androoting stimulants, chemosterilants, semiochemicals, repellents,attractants, pheromones, feeding stimulants, other biologically activecompounds or entomopathogenic bacteria, virus or fungi to form amulti-component pesticide giving an even broader spectrum of agronomicand nonagronomic utility. Thus the present invention also pertains to acomposition comprising a biologically effective amount of a compound ofFormula 1, at least one additional component selected from the groupconsisting of surfactants, solid diluents and liquid diluents, and atleast one additional biologically active compound or agent. For mixturesof the present invention, the other biologically active compounds oragents can be formulated together with the present compounds, includingthe compounds of Formula 1, to form a premix, or the other biologicallyactive compounds or agents can be formulated separately from the presentcompounds, including the compounds of Formula 1, and the twoformulations combined together before application (e.g., in a spraytank) or, alternatively, applied in succession.

Examples of such biologically active compounds or agents with whichcompounds of this invention can be formulated are insecticides such asabamectin, acephate, acequinocyl, acetamiprid, acrinathrin, afidopyropen([(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a, 12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methylcyclopropanecarboxylate), amidoflumet, amitraz, avermectin,azadirachtin, azinphos-methyl, benfuracarb, bensultap, bifenthrin,bifenazate, bistrifluron, borate, buprofezin, cadusafos, carbaryl,carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr,chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide,clofentezin, clothianidin, cyantraniliprole(3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide),cyclaniliprole (3-bromo-N-[2-bromo-4-chloro-6-[[(1-cyclopropylethyl)amino]carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide),cycloprothrin, cycloxaprid((5S,8R)-1-[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,8-hexahydro-9-nitro-5,8-Epoxy-1H-imidazo[1,2-a]azepine)cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon,dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate,dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenitrothion,fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil,flometoquin(2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolinylmethyl carbonate), flonicamid, flubendiamide, flucythrinate, flufenerim,flufenoxuron, flufenoxystrobin (methyl(αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)benzeneacetate),flufensulfone(5-chloro-2-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]thiazole),fluhexafon, fluopyram, flupiprole(1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-1-yl)amino]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile),flupyradifurone(4-[[(6-chloro-3-pyridinyl)methyl](2,2-difluoroethyl)amino]-2(5H)-furanone),fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate,halofenozide, heptafluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclopropanecarboxylate),hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb,insecticidal soaps, isofenphos, lufenuron, malathion, meperfluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl(1R,3S)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate),metaflumizone, metaldehyde, methamidophos, methidathion, methiodicarb,methomyl, methoprene, methoxychlor, metofluthrin, methoxyfenozide,metofluthrin, monocrotophos, monofluorothrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl3-(2-cyano-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate),nicotine, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl,parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet,phosphamidon, pirimicarb, profenofos, profluthrin, propargite,protrifenbute, pyflubumide(1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide),pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl,pyrifluquinazon, pyriminostrobin (methyl(αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)benzeneacetate),pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram,spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos,sulfoxaflor(N-[methyloxido[1-[6-(trifluoromethyl)-3-pyridinyl]ethyl]-?⁴-sulfanylidene]cyanamide),tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos,tetrachlorvinphos, tetramethrin, tetramethylfluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl2,2,3,3-tetramethylcyclopropanecarboxylate), tetraniliprole,thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tioxazafen(3-phenyl-5-(2-thienyl)-1,2,4-oxadiazole), tolfenpyrad, tralomethrin,triazamate, trichlorfon, triflumezopyrim(2,4-dioxo-1-(5-pyrimidinylmethyl)-3-[3-(trifluoromethyl)phenyl]-2H-pyrido[1,2-a]pyrimidiniuminner salt), triflumuron, Bacillus thuringiensis delta-endotoxins,entomopathogenic bacteria, entomopathogenic viruses and entomopathogenicfungi.

Of note are insecticides such as abamectin, acetamiprid, acrinathrin,afidopyropen, amitraz, avermectin, azadirachtin, benfuracarb, bensultap,bifenthrin, buprofezin, cadusafos, carbaryl, cartap,chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin,cyantraniliprole, cyclaniliprole, cycloprothrin, cyfluthrin,beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin,cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine,deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan,esfenvalerate, ethiprole, etofenprox, etoxazole, fenitrothion,fenothiocarb, fenoxycarb, fenvalerate, fipronil, flometoquin,flonicamid, flubendiamide, flufenoxuron, flufenoxystrobin,flufensulfone, flupiprole, flupyradifurone, fluvalinate, formetanate,fosthiazate, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid,indoxacarb, lufenuron, meperfluthrin, metaflumizone, methiodicarb,methomyl, methoprene, methoxyfenozide, metofluthrin, monofluorothrin,nitenpyram, nithiazine, novaluron, oxamyl, pyflubumide, pymetrozine,pyrethrin, pyridaben, pyridalyl, pyriminostrobin, pyriproxyfen,ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen,spirotetramat, sulfoxaflor, tebufenozide, tetramethrin,tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb,thiosultap-sodium, tralomethrin, triazamate, triflumezopyrim,triflumuron, Bacillus thuringiensis delta-endotoxins, all strains ofBacillus thuringiensis and all strains of nucleo polyhedrosis viruses.

One embodiment of biological agents for mixing with compounds of thisinvention include entomopathogenic bacteria such as Bacillusthuringiensis, and the encapsulated delta-endotoxins of Bacillusthuringiensis such as MVP® and MVPII® bioinsecticides prepared by theCellCap® process (CellCap®, MVP® and MVPII® are trademarks of MycogenCorporation, Indianapolis, Ind., USA); entomopathogenic fungi such asgreen muscardine fungus; and entomopathogenic (both naturally occurringand genetically modified) viruses including baculovirus, nucleopolyhedrovirus (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV),Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis virus(GV) such as Cydia pomonella granulosis virus (CpGV).

Of particular note is such a combination where the other invertebratepest control active ingredient belongs to a different chemical class orhas a different site of action than the compound of Formula 1. Incertain instances, a combination with at least one other invertebratepest control active ingredient having a similar spectrum of control buta different site of action will be particularly advantageous forresistance management. Thus, a composition of the present invention canfurther comprise a biologically effective amount of at least oneadditional invertebrate pest control active ingredient having a similarspectrum of control but belonging to a different chemical class orhaving a different site of action. These additional biologically activecompounds or agents include, but are not limited to,acetylcholinesterase (AChE) inhibitors such as the carbamates methomyl,oxamyl, thiodicarb, triazamate, and the organophosphates chlorpyrifos;GABA-gated chloride channel antagonists such as the cyclodienes dieldrinand endosulfan, and the phenylpyrazoles ethiprole and fipronil; sodiumchannel modulators such as the pyrethroids bifenthrin, cyfluthrin,beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin,deltamethrin, dimefluthrin, esfenvalerate, metofluthrin and profluthrin;nicotinic acetylcholinereceptor (nAChR) agonists such as theneonicotinoids acetamiprid, clothianidin, dinotefuran, imidacloprid,nitenpyram, nithiazine, thiacloprid, and thiamethoxam, and sulfoxaflor;nicotinic acetylcholine receptor (nAChR) allosteric activators such asthe spinosyns spinetoram and spinosad; chloride channel activators suchas the avermectins abamectin and emamectin; juvenile hormone mimics suchas diofenolan, methoprene, fenoxycarb and pyriproxyfen; selectivehomopteran feeding blockers such as pymetrozine and flonicamid; mitegrowth inhibitors such as etoxazole; inhibitors of mitochondrial ATPsynthase such as propargite; ucouplers of oxidative phosphorylation viadisruption of the proton gradient such as chlorfenapyr; nicotinicacetylcholine receptor (nAChR) channel blockers such as the nereistoxinanalogs cartap; inhibitors of chitin biosynthesis such as thebenzoylureas flufenoxuron, hexaflumuron, lufenuron, novaluron,noviflumuron and triflumuron, and buprofezin; dipteran moultingdisrupters such as cyromazine; ecdysone receptor agonists such as thediacylhydrazines methoxyfenozide and tebufenozide; octopamine receptoragonists such as amitraz; mitochondrial complex III electron transportinhibitors such as hydramethylnon; mitochondrial complex I electrontransport inhibitors such as pyridaben; voltage-dependent sodium channelblockers such as indoxacarb; inhibitors of acetyl CoA carboxylase suchas the tetronic and tetramic acids spirodiclofen, spiromesifen andspirotetramat; mitochondrial complex II electron transport inhibitorssuch as the ß-ketonitriles cyenopyrafen and cyflumetofen; ryanidinereceptor modulators such as the anthranilic diamideschlorantraniliprole, cyantraniliprole and cyantraniliprole, diamidessuch as flubendiamide, and ryanodine receptor ligands such as ryanodine;compounds wherein the target site responsible for biological activity isunknown or uncharacterized such as azadirachtin, bifenazate, pyridalyl,pyrifluquinazon and triflumezopyrim; microbial disrupters of insectmidgut membranes such as Bacillus thuringensis and the delta-endotoxinsthey produce and Bacillus sphaericus; and biological agents includingnucleo polyhedro viruses (NPV) and other naturally occurring orgenetically modified insecticidal viruses.

Further examples of biologically active compounds or agents with whichcompounds of this invention can be formulated are: fungicides such asacibenzolar-S-methyl, aldimorph, ametoctradin, amisulbrom, anilazine,azaconazole, azoxystrobin, benalaxyl (including benalaxyl-M), benodanil,benomyl, benthiavalicarb (including benthiavalicarb-isopropyl),benzovindiflupyr, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen,blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate,carboxin, carpropamid, captafol, captan, carbendazim, chloroneb,chlorothalonil, chlozolinate, copper hydroxide, copper oxychloride,copper sulfate, coumoxystrobin, cyazofamid, cyflufenamid, cymoxanil,cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine,dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol,dimethomorph, dimoxystrobin, diniconazole (including diniconazole-M),dinocap, dithianon, dithiolanes, dodemorph, dodine, econazole,etaconazole, edifenphos, enoxastrobin (also known as enestroburin),epoxiconazole, ethaboxam, ethirimol, etridiazole, famoxadone,fenamidone, fenaminstrobin, fenarimol, fenbuconazole, fenfuram,fenhexamide, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph,fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone,flometoquin, fluazinam, fludioxonil, flufenoxystrobin, flumorph,fluopicolide, fluopyram, fluoxastrobin, fluquinconazole, flusilazole,flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet,fthalide (also known as phthalide), fuberidazole, furalaxyl, furametpyr,hexaconazole, hymexazole, guazatine, imazalil, imibenconazole,iminoctadine albesilate, iminoctadine triacetate, iodicarb, ipconazole,isofetamid, iprobenfos, iprodione, iprovalicarb, isoprothiolane,isopyrazam, isotianil, kasugamycin, kresoxim-methyl, mancozeb,mandipropamid, mandestrobin, maneb, mapanipyrin, mepronil,meptyldinocap, metalaxyl (including metalaxyl-M/mefenoxam), metconazole,methasulfocarb, metiram, metominostrobin, metrafenone, myclobutanil,naftitine, neo-asozin (ferric methanearsonate), nuarimol, octhilinone,ofurace, orysastrobin, oxadixyl, oxathiapiprolin, oxolinic acid,oxpoconazole, oxycarboxin, oxytetracycline, penconazole, pencycuron,penflufen, penthiopyrad, perfurazoate, phosphorous acid (including saltsthereof, e.g., fosetyl-aluminm), picoxystrobin, piperalin, polyoxin,probenazole, prochloraz, procymidone, propamocarb, propiconazole,propineb, proquinazid, prothiocarb, prothioconazole, pyraclostrobin,pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributacarb,pyrifenox, pyriofenone, perisoxazole, pyrimethanil, pyrifenox,pyrrolnitrin, pyroquilon, quinconazole, quinmethionate, quinoxyfen,quintozene, silthiofam, sedaxane, simeconazole, spiroxamine,streptomycin, sulfur, tebuconazole, tebufloquin, teclofthalam,tecloftalam, tecnazene, terbinafine, tetraconazole, thiabendazole,thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil,tolclofos-methyl, tolprocarb, tolyfluanid, triadimefon, triadimenol,triarimol, triazoxide, tribasic copper sulfate, triclopyricarb,tridemorph, trifloxystrobin, triflumizole, trimoprhamide tricyclazole,trifloxystrobin, triforine, triticonazole, uniconazole, validamycin,valifenalate (also known as valifenal), vinclozolin, zineb, ziram,zoxamide and1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone;nematocides such as fluopyram, spirotetramat, thiodicarb, fosthiazate,abamectin, iprodione, fluensulfone, dimethyl disulfide, tioxazafen,1,3-dichloropropene (1,3-D), metam (sodium and potassium), dazomet,chloropicrin, fenamiphos, ethoprophos, cadusaphos, terbufos, imicyafos,oxamyl, carbofuran, tioxazafen, Bacillus firmus and Pasteurianishizawae; bactericides such as streptomycin; acaricides such asamitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol,dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin,fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad.

In certain instances, combinations of a compound of this invention withother biologically active (particularly invertebrate pest control)compounds or agents (i.e. active ingredients) can result in agreater-than-additive (i.e. synergistic) effect. Reducing the quantityof active ingredients released in the environment while ensuringeffective pest control is always desirable. When synergism ofinvertebrate pest control active ingredients occurs at application ratesgiving agronomically satisfactory levels of invertebrate pest control,such combinations can be advantageous for reducing crop production costand decreasing environmental load.

Compounds of this invention and compositions thereof can be applied toplants genetically transformed to express proteins toxic to invertebratepests (such as Bacillus thuringiensis delta-endotoxins). Such anapplication may provide a broader spectrum of plant protection and beadvantageous for resistance management. The effect of the exogenouslyapplied invertebrate pest control compounds of this invention may besynergistic with the expressed toxin proteins.

General references for these agricultural protectants (i.e.insecticides, fungicides, nematocides, acaricides, herbicides andbiological agents) include The Pesticide Manual, 13th Edition, C. D. S.Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U. K.,2003 and The BioPesticide Manual, 2^(nd) Edition, L. G. Copping, Ed.,British Crop Protection Council, Farnham, Surrey, U. K., 2001.

Invertebrate pests are controlled in agronomic and nonagronomicapplications by applying one or more compounds of this invention,typically in the form of a composition, in a biologically effectiveamount, to the environment of the pests, including the agronomic and/ornonagronomic locus of infestation, to the area to be protected, ordirectly on the pests to be controlled.

Thus the present invention comprises a method for controlling aninvertebrate pest in agronomic and/or nonagronomic applications,comprising contacting the invertebrate pest or its environment with abiologically effective amount of one or more of the compounds of theinvention, or with a composition comprising at least one such compoundor a composition comprising at least one such compound and abiologically effective amount of at least one additional biologicallyactive compound or agent. Examples of suitable compositions comprising acompound of the invention and a biologically effective amount of atleast one additional biologically active compound or agent includegranular compositions wherein the additional active compound is presenton the same granule as the compound of the invention or on granulesseparate from those of the compound of the invention.

To achieve contact with a compound or composition of the invention toprotect a field crop from invertebrate pests, the compound orcomposition is typically applied to the seed of the crop beforeplanting, to the foliage (e.g., leaves, stems, flowers, fruits) of cropplants, or to the soil or other growth medium before or after the cropis planted.

One embodiment of a method of contact is by spraying. Alternatively, agranular composition comprising a compound of the invention can beapplied to the plant foliage or the soil. Compounds of this inventioncan also be effectively delivered through plant uptake by contacting theplant with a composition comprising a compound of this invention appliedas a soil drench of a liquid formulation, a granular formulation to thesoil, a nursery box treatment or a dip of transplants. Of note is acomposition of the present invention in the form of a soil drench liquidformulation. Also of note is a method for controlling an invertebratepest comprising contacting the invertebrate pest or its environment witha biologically effective amount of a compound of the present inventionor with a composition comprising a biologically effective amount of acompound of the present invention. Of further note is this methodwherein the environment is soil and the composition is applied to thesoil as a soil drench formulation. Of further note is that compounds ofthis invention are also effective by localized application to the locusof infestation. Other methods of contact include application of acompound or a composition of the invention by direct and residualsprays, aerial sprays, gels, seed coatings, microencapsulations,systemic uptake, baits, ear tags, boluses, foggers, fumigants, aerosols,dusts and many others. One embodiment of a method of contact is adimensionally stable fertilizer granule, stick or tablet comprising acompound or composition of the invention. The compounds of thisinvention can also be impregnated into materials for fabricatinginvertebrate control devices (e.g., insect netting).

Compounds of the invention are useful in treating all plants, plantparts and seeds. Plant and seed varieties and cultivars can be obtainedby conventional propagation and breeding methods or by geneticengineering methods. Genetically modified plants or seeds (transgenicplants or seeds) are those in which a heterologous gene (transgene) hasbeen stably integrated into the plant's or seed's genome. A transgenethat is defined by its particular location in the plant genome is calleda transformation or transgenic event.

Genetically modified plant and seed cultivars which can be treatedaccording to the invention include those that are resistant against oneor more biotic stresses (pests such as nematodes, insects, mites, fungi,etc.) or abiotic stresses (drought, cold temperature, soil salinity,etc.), or that contain other desirable characteristics. Plants and seedscan be genetically modified to exhibit traits of, for example, herbicidetolerance, insect-resistance, modified oil profiles or droughttolerance.

Treatment of genetically modified plants and seeds with compounds of theinvention may result in super-additive or synergistic effects. Forexample, reduction in application rates, broadening of the activityspectrum, increased tolerance to biotic/abiotic stresses or enhancedstorage stability may be greater than expected from just simple additiveeffects of the application of compounds of the invention on geneticallymodified plants and seeds.

Compounds of this invention are also useful in seed treatments forprotecting seeds from invertebrate pests. In the context of the presentdisclosure and claims, treating a seed means contacting the seed with abiologically effective amount of a compound of this invention, which istypically formulated as a composition of the invention. This seedtreatment protects the seed from invertebrate soil pests and generallycan also protect roots and other plant parts in contact with the soil ofthe seedling developing from the germinating seed. The seed treatmentmay also provide protection of foliage by translocation of the compoundof this invention or a second active ingredient within the developingplant. Seed treatments can be applied to all types of seeds, includingthose from which plants genetically transformed to express specializedtraits will germinate. Representative examples include those expressingproteins toxic to invertebrate pests, such as Bacillus thuringiensistoxin or those expressing herbicide resistance such as glyphosateacetyltransferase, which provides resistance to glyphosate. Seedtreatments with compounds of this invention can also increase vigor ofplants growing from the seed.

One method of seed treatment is by spraying or dusting the seed with acompound of the invention (i.e. as a formulated composition) beforesowing the seeds. Compositions formulated for seed treatment generallycomprise a film former or adhesive agent. Therefore typically a seedcoating composition of the present invention comprises a biologicallyeffective amount of a compound of Formula 1, an N-oxide or salt thereof,and a film former or adhesive agent. Seed can be coated by spraying aflowable suspension concentrate directly into a tumbling bed of seedsand then drying the seeds. Alternatively, other formulation types suchas wetted powders, solutions, suspoemulsions, emulsifiable concentratesand emulsions in water can be sprayed on the seed. This process isparticularly useful for applying film coatings on seeds. Various coatingmachines and processes are available to one skilled in the art. Suitableprocesses include those listed in P. Kosters et al., Seed Treatment:Progress and Prospects, 1994 BCPC Mongraph No. 57, and references listedtherein.

Compounds of Formula 1 and their compositions, both alone and incombination with other insecticides, nematicides, and fungicides, areparticularly useful in seed treatment for crops including, but notlimited to, maize or corn, soybeans, cotton, cereal (e.g., wheat, oats,barley, rye and rice), potatoes, vegetables and oilseed rape.

Other insecticides with which compounds of Formula 1 can be formulatedto provide mixtures useful in seed treatment include abamectin,acetamiprid, acrinathrin, amitraz, avermectin, azadirachtin, bensultap,bifenthrin, buprofezin, cadusafos, carbaryl, carbofuran, cartap,chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin,cyantraniliprole, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran,diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox,etoxazole, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flonicamid,flubendiamide, flufenoxuron, fluvalinate, formetanate, fosthiazate,hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron,metaflumizone, methiocarb, methomyl, methoprene, methoxyfenozide,nitenpyram, nithiazine, novaluron, oxamyl, pymetrozine, pyrethrin,pyridaben, pyridalyl, pyriproxyfen, ryanodine, spinetoram, spinosad,spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide,tetramethrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium,tralomethrin, triazamate, triflumuron, Bacillus thuringiensisdelta-endotoxins, all strains of Bacillus thuringiensis and all strainsof nucleo polyhedrosis viruses.

Fungicides with which compounds of Formula 1 can be formulated toprovide mixtures useful in seed treatment include amisulbrom,azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil, cyproconazole,difenoconazole, dimethomorph, fluazinam, fludioxonil, fluquinconazole,fluopicolide, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole,iprodione, metalaxyl, mefenoxam, metconazole, myclobutanil,paclobutrazole, penflufen, picoxystrobin, prothioconazole,pyraclostrobin, sedaxane, silthiofam, tebuconazole, thiabendazole,thiophanate-methyl, thiram, trifloxystrobin and triticonazole.

Compositions comprising compounds of Formula 1 useful for seed treatmentcan further comprise bacteria and fungi that have the ability to provideprotection from the harmful effects of plant pathogenic fungi orbacteria and/or soil born animals such as nematodes. Bacteria exhibitingnematicidal properties may include but are not limited to Bacillusfirmus, Bacillus cereus, Bacillius subtiliis and Pasteuria penetrans. Asuitable Bacillus firmus strain is strain CNCM I-1582 (GB-126) which iscommercially available as BioNem™. A suitable Bacillus cereus strain isstrain NCMM I-1592. Both Bacillus strains are disclosed in U.S. Pat. No.6,406,690. Other suitable bacteria exhibiting nematicidal activity areB. amyloliquefaciens IN937a and B. subtilis strain GB03. Bacteriaexhibiting fungicidal properties may include but are not limited to B.pumilus strain GB34. Fungal species exhibiting nematicidal propertiesmay include but are not limited to Myrothecium verrucaria, Paecilomyceslilacinus and Purpureocillium lilacinum.

Seed treatments can also include one or more nematicidal agents ofnatural origin such as the elicitor protein called harpin which isisolated from certain bacterial plant pathogens such as Erwiniaamylovora. An example is the Harpin-N-Tek seed treatment technologyavailable as N-Hibit™ Gold CST.

Seed treatments can also include one or more species of legume-rootnodulating bacteria such as the microsymbiotic nitrogen-fixing bacteriaBradyrhizobium japonicum. These inocculants can optionally include oneor more lipo-chitooligosaccharides (LCOs), which are nodulation (Nod)factors produced by rhizobia bacteria during the initiation of noduleformation on the roots of legumes. For example, the Optimize® brand seedtreatment technology incorporates LCO Promoter Technology™ incombination with an inocculant.

Seed treatments can also include one or more isoflavones which canincrease the level of root colonization by mycorrhizal fungi.Mycorrhizal fungi improve plant growth by enhancing the root uptake ofnutrients such as water, sulfates, nitrates, phosphates and metals.Examples of isoflavones include, but are not limited to, genistein,biochanin A, formononetin, daidzein, glycitein, hesperetin, naringeninand pratensein. Formononetin is available as an active ingredient inmycorrhizal inocculant products such as PHC Colonize® AG.

Seed treatments can also include one or more plant activators thatinduce systemic acquired resistance in plants following contact by apathogen. An example of a plant activator which induces such protectivemechanisms is acibenzolar-S-methyl.

The treated seed typically comprises a compound of the present inventionin an amount from about 0.1 g to 1 kg per 100 kg of seed (i.e. fromabout 0.0001 to 1% by weight of the seed before treatment). A flowablesuspension formulated for seed treatment typically comprises from about0.5 to about 70% of the active ingredient, from about 0.5 to about 30%of a film-forming adhesive, from about 0.5 to about 20% of a dispersingagent, from 0 to about 5% of a thickener, from 0 to about 5% of apigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0to about 1% of a preservative, and from 0 to about 75% of a volatileliquid diluent.

The compounds of this invention can be incorporated into a baitcomposition that is consumed by an invertebrate pest or used within adevice such as a trap, bait station, and the like. Such a baitcomposition can be in the form of granules which comprise (a) activeingredients, namely a biologically effective amount of a compound ofFormula 1, an N-oxide, or salt thereof; (b) one or more food materials;optionally (c) an attractant, and optionally (d) one or more humectants.Of note are granules or bait compositions which comprise between about0.001-5% active ingredients, about 40-99% food material and/orattractant; and optionally about 0.05-10% humectants, which areeffective in controlling soil invertebrate pests at very low applicationrates, particularly at doses of active ingredient that are lethal byingestion rather than by direct contact. Some food materials canfunction both as a food source and an attractant. Food materials includecarbohydrates, proteins and lipids. Examples of food materials arevegetable flour, sugar, starches, animal fat, vegetable oil, yeastextracts and milk solids. Examples of attractants are odorants andflavorants, such as fruit or plant extracts, perfume, or other animal orplant component, pheromones or other agents known to attract a targetinvertebrate pest. Examples of humectants, i.e. moisture retainingagents, are glycols and other polyols, glycerine and sorbitol. Of noteis a bait composition (and a method utilizing such a bait composition)used to control at least one invertebrate pest selected from the groupconsisting of ants, termites and cockroaches. A device for controllingan invertebrate pest can comprise the present bait composition and ahousing adapted to receive the bait composition, wherein the housing hasat least one opening sized to permit the invertebrate pest to passthrough the opening so the invertebrate pest can gain access to the baitcomposition from a location outside the housing, and wherein the housingis further adapted to be placed in or near a locus of potential or knownactivity for the invertebrate pest.

One embodiment of the present invention relates to a method forcontrolling invertebrate pests, comprising diluting the pesticidalcomposition of the present invention (a compound of Formula 1 formulatedwith surfactants, solid diluents and liquid diluents or a formulatedmixture of a compound of Formula 1 and at least one other pesticide)with water, and optionally adding an adjuvant to form a dilutedcomposition, and contacting the invertebrate pest or its environmentwith an effective amount of said diluted composition.

Although a spray composition formed by diluting with water a sufficientconcentration of the present pesticidal composition can providesufficient efficacy for controlling invertebrate pests, separatelyformulated adjuvant products can also be added to spray tank mixtures.These additional adjuvants are commonly known as “spray adjuvants” or“tank-mix adjuvants”, and include any substance mixed in a spray tank toimprove the performance of a pesticide or alter the physical propertiesof the spray mixture. Adjuvants can be surfactants, emulsifying agents,petroleum-based crop oils, crop-derived seed oils, acidifiers, buffers,thickeners or defoaming agents. Adjuvants are used to enhancing efficacy(e.g., biological availability, adhesion, penetration, uniformity ofcoverage and durability of protection), or minimizing or eliminatingspray application problems associated with incompatibility, foaming,drift, evaporation, volatilization and degradation. To obtain optimalperformance, adjuvants are selected with regard to the properties of theactive ingredient, formulation and target (e.g., crops, insect pests).

Among the spray adjuvants, oils including crop oils, crop oilconcentrates, vegetable oil concentrates and methylated seed oilconcentrates are most commonly used to improve the efficacy ofpesticides, possibly by means of promoting more even and uniform spraydeposits. In situations where phytotoxicity potentially caused by oilsor other water-immiscible liquids are of concern, spray compositionsprepared from the composition of the present invention will generallynot contain oil-based spray adjuvants. However, in situations wherephytotoxicity caused by oil-based spray adjuvants is commerciallyinsignificant, spray compositions prepared from the composition of thepresent composition can also contain oil-based spray adjuvants, whichcan potentially further increase control of invertebrate pests, as wellas rainfastness.

Products identified as “crop oil” typically contain 95 to 98% paraffinor naphtha-based petroleum oil and 1 to 2% of one or more surfactantsfunctioning as emulsifiers. Products identified as “crop oilconcentrates” typically consist of 80 to 85% of emulsifiablepetroleum-based oil and 15 to 20% of nonionic surfactants. Productscorrectly identified as “vegetable oil concentrates” typically consistof 80 to 85% of vegetable oil (i.e. seed or fruit oil, most commonlyfrom cotton, linseed, soybean or sunflower) and 15 to 20% of nonionicsurfactants. Adjuvant performance can be improved by replacing thevegetable oil with methyl esters of fatty acids that are typicallyderived from vegetable oils. Examples of methylated seed oilconcentrates include MSO® Concentrate (UAP-Loveland Products, Inc.) andPremium MSO Methylated Spray Oil (Helena Chemical Company).

The amount of adjuvants added to spray mixtures generally does notexceed about 2.5% by volume, and more typically the amount is from about0.1 to about 1% by volume. The application rates of adjuvants added tospray mixtures are typically between about 1 to 5 L per hectare.Representative examples of spray adjuvants include: Adigor® (Syngenta)47% methylated rapeseed oil in liquid hydrocarbons, Silwet® (HelenaChemical Company) polyalkyleneoxide modified heptamethyltrisiloxane andAssist® (BASF) 17% surfactant blend in 83% paraffin based mineral oil.

The compounds of this invention can be applied without other adjuvants,but most often application will be of a formulation comprising one ormore active ingredients with suitable carriers, diluents, andsurfactants and possibly in combination with a food depending on thecontemplated end use. One method of application involves spraying awater dispersion or refined oil solution of a compound of the presentinvention. Combinations with spray oils, spray oil concentrations,spreader stickers, adjuvants, other solvents, and synergists such aspiperonyl butoxide often enhance compound efficacy. For nonagronomicuses such sprays can be applied from spray containers such as a can, abottle or other container, either by means of a pump or by releasing itfrom a pressurized container, e.g., a pressurized aerosol spray can.

Such spray compositions can take various forms, for example, sprays,mists, foams, fumes or fog. Such spray compositions thus can furthercomprise propellants, foaming agents, etc. as the case may be. Of noteis a spray composition comprising a biologically effective amount of acompound or a composition of the present invention and a carrier. Oneembodiment of such a spray composition comprises a biologicallyeffective amount of a compound or a composition of the present inventionand a propellant. Representative propellants include, but are notlimited to, methane, ethane, propane, butane, isobutane, butene,pentane, isopentane, neopentane, pentene, hydrofluorocarbons,chlorofluorocarbons, dimethyl ether, and mixtures of the foregoing. Ofnote is a spray composition (and a method utilizing such a spraycomposition dispensed from a spray container) used to control at leastone invertebrate pest selected from the group consisting of mosquitoes,black flies, stable flies, deer flies, horse flies, wasps, yellowjackets, hornets, ticks, spiders, ants, gnats, and the like, includingindividually or in combinations.

The following Tests demonstrate the control efficacy of compounds ofthis invention on specific pests. “Control efficacy” representsinhibition of invertebrate pest development (including mortality) thatcauses significantly reduced feeding. The pest control protectionafforded by the compounds is not limited, however, to these species. SeeIndex Tables A-G for compound descriptions.

Biological Examples of the Invention Formulation and Spray Methodologyfor Tests A-F

Test compounds were formulated using a solution containing 10% acetone,90% water and 300 ppm X-77® Spreader Lo-Foam Formula non-ionicsurfactant containing alkylarylpolyoxyethylene, free fatty acids,glycols and isopropanol (Loveland Industries, Inc. Greeley, Colo., USA).The formulated compounds were applied in 1 mL of liquid through a SUJ2atomizer nozzle with 1/8 JJ custom body (Spraying Systems Co. Wheaton,Ill., USA) positioned 1.27 cm (0.5 inches) above the top of each testunit. Test compounds were sprayed at the rates indicated, and each testwas replicated three times.

Test A

For evaluating control of diamondback moth (Plutella xylostella (L.))the test unit consisted of a small open container with a 12-14-day-oldmustard plant inside. This was pre-infested with ˜50 neonate larvae thatwere dispensed into the test unit via corn cob grits using aninoculator. The larvae moved onto the test plant after being dispensedinto the test unit.

Test compounds were formulated and sprayed at 250. After spraying of theformulated test compound, each test unit was allowed to dry for 1 hourand then a black, screened cap was placed on top. The test units wereheld for 6 days in a growth chamber at 25° C. and 70% relative humidity.Plant feeding damage was then visually assessed based on foliageconsumed, and larvae were assessed for mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following providedvery good to excellent levels of control efficacy (40% or less feedingdamage and/or 100% mortality): 11 and 111.

Test B

For evaluating control of green peach aphid (Myzus persicae (Sulzer))through contact and/or systemic means, the test unit consisted of asmall open container with a 12-15-day-old radish plant inside. This waspre-infested by placing on a leaf of the test plant 30-40 aphids on apiece of leaf excised from a culture plant (cut-leaf method). The aphidsmoved onto the test plant as the leaf piece desiccated. Afterpre-infestation, the soil of the test unit was covered with a layer ofsand.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. Afterspraying of the formulated test compound, each test unit was allowed todry for 1 hour and then a black, screened cap was placed on top. Thetest units were held for 6 days in a growth chamber at 19-21° C. and50-70% relative humidity. Each test unit was then visually assessed forinsect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following resultedin at least 80% mortality: 10, 11, 12, 19, 20, 22, 24, 25, 26, 29, 31,35, 36, 39, 43, 45, 46, 60, 61, 62, 64, 65, 66, 71, 72, 73, 74, 75, 78and 79.

Of the compounds of Formula 1 tested at 50 ppm, the following resultedin at least 80% mortality: 10, 11, 12, 20, 24, 25, 26, 29, 30, 31, 35,45, 46, 47, 56, 58, 59, 60, 61, 62, 64, 65, 66, 68, 69, 70, 71, 72, 73,74, 75, 78, 79, 80, 84, 85, 86, 87, 96, 102, 103, 104, 106, 107, 122,123, 125, 135, 137, 139, 145, 146, 151, 153, 154, 155, 156, 158, 160,161, 162 and 163.

Test C

For evaluating control of cotton melon aphid (Aphis gossypii (Glover))through contact and/or systemic means, the test unit consisted of asmall open container with a 6-7-day-old cotton plant inside. This waspre-infested with 30-40 insects on a piece of leaf according to thecut-leaf method, and the soil of the test unit was covered with a layerof sand.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. Afterspraying, the test units were maintained in a growth chamber for 6 daysat 19° C. and 70% relative humidity. Each test unit was then visuallyassessed for insect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following resultedin at least 80% mortality: 10, 11, 12, 15, 16, 17, 18, 19, 20, 21, 22,23, 24, 25, 26, 29, 31, 33, 34, 35, 37, 38, 45, 46, 62, 64, 65, 66, 71,72, 76 and 77.

Of the compounds of Formula 1 tested at 50 ppm, the following resultedin at least 80% mortality: 10, 11, 12, 15, 16, 17, 18, 19, 20, 21, 22,23, 24, 25, 26, 29, 30, 31, 33, 34, 35, 45, 46, 47, 52, 54, 56, 59, 62,64, 65, 66, 67, 69, 70, 71, 72, 76, 77, 78, 80, 84, 85, 86, 87, 96, 101,102, 103, 104, 105, 106, 107, 112, 114, 119, 122, 123, 125, 128, 129,131, 135, 137, 139, 145, 146, 151, 154, 155, 156, 158, 160, 161, 162,163, 164 and 169.

Test D

For evaluating control of potato leafhopper (Empoasca fabae (Harris))through contact and/or systemic means, the test unit consisted of asmall open container with a 5-6-day-old Soleil bean plant (primaryleaves emerged) inside. White sand was added to the top of the soil, andone of the primary leaves was excised prior to application of the testcompound.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. Afterspraying of the formulated test compound, the test units were allowed todry for 1 hour before they were post-infested with 5 potato leafhoppers(18-to-21-day-old adults). A black, screened cap was placed on the topof the test unit, and the test units were held for 6 days in a growthchamber at 20° C. and 70% relative humidity. Each test unit was thenvisually assessed for insect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following resultedin at least 80% mortality: 80, 81, 83 and 163.

Test E

For evaluating control of the sweetpotato whitefly (Bemisia tabaci(Gennadius)) through contact and/or systemic means, the test unitconsisted of a small open container with a 12-14-day-old cotton plantinside. Prior to the spray application, both cotyledons were removedfrom the plant, leaving one true leaf for the assay. Adult whiteflieswere allowed to lay eggs on the plant and then were removed from thetest unit. Cotton plants infested with at least 15 eggs were submittedto the test for spraying.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. Afterspraying, the test units were allowed to dry for 1 hour. The cylinderswere then removed, and the units were taken to a growth chamber and heldfor 13 days at 28° C. and 50-70% relative humidity. Each test unit wasthen visually assessed for insect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following resultedin at least 50% mortality: 2, 12, 25, 29, 47, 48, 55, 56, 57, 58, 59,62, 64, 84, 102, 104 and 106.

Of the compounds of Formula 1 tested at 50 ppm, the following resultedin at least 50% mortality: 24, 25, 47, 62, 65, 66, 102 and 104.

Test F

For evaluating control of the Western Flower Thrips (Franklinielllaoccidentalis (Pergande)) through contact and/or systemic means, the testunit consisted of a small open container with a 5-7-day-old Soleil beanplant inside.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. Afterspraying, the test units were allowed to dry for 1 hour, and then 22-27adult thrips were added to each unit. A black, screened cap was placedon top, and the test units were held for 6 days at 25° C. and 45-55%relative humidity.

Of the compounds of Formula 1 tested at 250 ppm, the following providedvery good to excellent levels of control efficacy (30% or less plantdamage and/or 100% mortality): 18, 29, 31, 79 and 90.

Of the compounds of Formula 1 tested at 50 ppm, the following providedvery good to excellent levels of control efficacy (30% or less plantdamage and/or 100% mortality): 18.

What is claimed is:
 1. A compound selected from Formula 1, an N-oxide orsalt thereof,

wherein A is CH, CF or N; X¹ is CR¹, and X² is CR² or N; or X¹ is CR² orN, and X² is CR¹; X³ is CR² or N; R¹ is a 5- to 10-membered aromaticring or ring system, each ring or ring system containing ring membersselected from carbon atoms and up to 3 heteroatoms independentlyselected from one oxygen atom, one sulfur atom, and up to 3 nitrogenatoms, wherein up to 2 carbon atom ring members are independentlyselected from C(═O) and C(═S) and the sulfur atom ring member isselected from S, S(O) or S(O)₂, each ring or ring system beingsubstituted with one R³, and optionally further substituted with 1 to 3R^(x); or R¹ is a 3- to 6-membered partially saturated ring, each ringcontaining ring members selected from carbon atoms and up to 2heteroatoms independently selected from one oxygen atom, one sulfuratom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ringmembers are independently selected from C(═O) and C(═S) and the sulfuratom ring member is selected from S, S(O) or S(O)₂, each ring beingsubstituted with one R³, and optionally further substituted with atleast one R^(x); each R² is independently H, halogen, cyano, nitro,C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy; R³ isselected from the group consisting of

each R⁴ is independently H or C₁-C₄ alkyl; each R⁵ is independently H orC₁-C₄ alkyl; or R⁴ and R⁵ are taken together with the carbon atom towhich they are attached to form a 3- to 6-membered ring containing ringmembers selected from carbon atoms and up to 2 heteroatoms independentlyselected from one oxygen atom, one sulfur atom, and up to 2 nitrogenatoms, wherein up to 2 carbon atom ring members are independentlyselected from C(═O) and C(═S) and the sulfur atom ring member isselected from S, S(O) or S(O)₂, said ring being unsubstituted orsubstituted with up to 4 R^(x); provided that R⁴ and R⁵ are attached tothe same carbon atom; p is 1, 2, 3 or 4; R⁶ is H, NR¹³R¹⁴, OR¹⁵ orC(═NR⁸)R⁹; or C₁-C₆ alkyl substituted with at least one R^(y); or C₃-C₆cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted orsubstituted with at least one R^(x); R^(6a) is OC(═NR⁸)R⁹, OC(O)R⁹,NHC(═NR⁸)R⁹, NHC(O)R⁹, SO₂NR¹³R¹⁴, SO₂OR¹⁵, SO₂C(═NR⁸)R⁹,C(═NR⁸)NR¹³R¹⁴, C(O)NR¹³R⁴, C(═NR⁸)OR⁵ or C(O)OR¹⁵; or R^(6a) isYR^(6b); Y is O, S, NH or C(O); R^(6b) is C₁-C₆ alkyl substituted withat least one R^(y); or C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl,each unsubstituted or substituted with at least one R^(x); R⁷ is H,C(O)R¹⁷ or S(O)_(n)R¹⁸; or C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₃-C₆cycloalkoxy, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted orsubstituted with at least one R^(x); or phenyl or a 5- or 6-memberedheterocyclic aromatic ring, or a 5- or 6-membered heterocyclicnon-aromatic ring, each unsubstituted or substituted with at least onesubstituent independently selected from the group consisting of halogen,cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄alkoxy, C₃-C₆ cycloalkoxy and C₁-C₄ haloalkoxy; provided that when R³ isR^(3b), R^(3d), R^(3e) or R^(3f), then both R⁶ and R⁷ cannot be H; eachR^(x) is independently halogen, cyano, nitro, hydroxy, C₁-C₆ alkyl,C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₃-C₆cycloalkoxy, C(═NR⁸)R⁹, C(O)OR¹⁶, C(O)NR¹³R¹⁴, OC(O)R¹⁷, NR²⁰R²¹,NR¹⁹C(O)R¹⁷, C(O)R¹⁷, S(O)_(n)R¹⁸, Si(R²³)₃, OSi(R²³)₃ or Q; each R^(y)is independently cyano, nitro, hydroxy, C₁-C₆ alkyl, C₁-C₆ haloalkyl,C₃-C₆ cycloalkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₃-C₆ cycloalkoxy,C(═NR⁸)R⁹, C(O)OR¹⁶, C(O)NR¹³R¹⁴, OC(O)R¹⁷, NR²⁰R²¹, NR¹⁹C(O)R¹⁷,C(O)R¹⁷, S(O)_(n)R¹⁸, Si(R²³)₃, OSi(R²³)₃ or Q; each R⁸ is independentlyOR¹⁰, S(O)_(n)R¹¹ or NHR²; each R⁹ is independently H; or C₁-C₆ alkyl,C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted orsubstituted with at least one R^(x); or C₁-C₆ alkoxy, C₁-C₆ haloalkoxy,C₃-C₆ cycloalkoxy, C(O)OR¹⁶, C(O)NR¹³R¹⁴, NR²⁰R²¹, NR¹⁹C(O)R¹⁷, C(O)R¹⁷or Q; each R¹⁰ is independently C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄haloalkyl, C(O)R¹⁷, S(O)_(n)R¹¹ or Q; each R¹¹ is independently C₁-C₄alkyl or C₁-C₄ haloalkyl; R¹² is C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄haloalkyl, C(O)R¹⁷ or C(O)OR¹⁶; or phenyl, unsubstituted or substitutedwith at least one substituent independently selected from the groupconsisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl,C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; each R¹³ isindependently H, C₁-C₆ alkyl, C₁-C₄ haloalkyl, C₁-C₄ hydroxyalkyl,C(O)R²² or S(O)₂R²²; or phenyl or a 5- or 6-membered heterocyclicaromatic ring, each unsubstituted or substituted with at least onesubstituent independently selected from the group consisting of halogen,cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄alkoxy and C₁-C₄ haloalkoxy; each R¹⁴ is independently H, C₁-C₆ alkyl orC₁-C₄ haloalkyl; or R¹³ and R¹⁴ are taken together with the nitrogenatom to which they are attached to form a 3- to 7-membered ringcontaining ring members selected from carbon atoms and up to 2heteroatoms independently selected from one oxygen atom, one sulfuratom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ringmembers are independently selected from C(═O) and C(═S) and the sulfuratom ring member is selected from S, S(O) or S(O)₂, said ring beingunsubstituted or substituted with at least one substituent independentlyselected from the group consisting of halogen, cyano, nitro, C₁-C₄alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄haloalkoxy; R¹⁵ is C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₃-C₆ cycloalkoxy orC₁-C₄ haloalkyl; or phenyl, unsubstituted or substituted with at leastone substituent independently selected from the group consisting ofhalogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl,C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; each R¹⁶ is independently H, C₁-C₄alkyl, C₁-C₄ haloalkyl, C₃-C₆ cycloalkyl or C₃-C₆ halocycloalkyl; orphenyl, unsubstituted or substituted with at least one substituentindependently selected from the group consisting of halogen, cyano,nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy andC₁-C₄ haloalkoxy; each R¹⁷ is independently C₁-C₄ alkyl, C₁-C₄haloalkyl, C₃-C₆ cycloalkyl or C₃-C₆ halocycloalkyl; or phenyl,unsubstituted or substituted with at least one substituent independentlyselected from the group consisting of halogen, cyano, nitro, C₁-C₄alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄haloalkoxy; each R¹⁸ is independently C₁-C₄ alkyl, C₁-C₄ haloalkyl,C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ cycloalkylalkyl or C₃-C₆halocycloalkylalkyl; or phenyl, unsubstituted or substituted with atleast one substituent independently selected from the group consistingof halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; each R¹⁹ is independentlyH or C₁-C₄ alkyl; each R²⁰ is independently H, C₁-C₄ alkyl or C₁-C₄haloalkyl; or phenyl, unsubstituted or substituted with at least onesubstituent independently selected from the group consisting of halogen,cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄alkoxy and C₁-C₄ haloalkoxy; each R²¹ is independently H, C₁-C₄ alkyl orC₁-C₄ haloalkyl; or phenyl, unsubstituted or substituted with at leastone substituent independently selected from the group consisting ofhalogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl,C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; or R²⁰ and R²¹ are independentlytaken together with the nitrogen atom to which they are attached to forma 3- to 7-membered ring containing ring members selected from carbonatoms and up to 2 heteroatoms independently selected from one oxygenatom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2carbon atom ring members are independently selected from C(═O) and C(═S)and the sulfur atom ring member is selected from S, S(O) or S(O)₂, saidring being unsubstituted or substituted with at least one substituentindependently selected from the group consisting of halogen, cyano,nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy andC₁-C₄ haloalkoxy; each R²² is independently C₁-C₆ alkyl, C₁-C₆haloalkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy or NR²⁴R²⁵; or phenyl or a 5-or 6-membered heterocyclic aromatic ring, each unsubstituted orsubstituted with at least one substituent independently selected fromthe group consisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; each R²³is independently C₁-C₆ alkyl, C₃-C₆ cycloalkyl or phenyl; each R²⁴ isindependently H or Q; or C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl orC₂-C₆ alkynyl, each unsubstituted or substituted with at least onesubstituent independently selected from the group consisting of halogen,cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄alkoxy and C₁-C₄ haloalkoxy; each R²⁵ is independently H or Q; or C₁-C₆alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, eachunsubstituted or substituted with at least one substituent independentlyselected from the group consisting of halogen, cyano, nitro, C₁-C₄alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄haloalkoxy; or R²⁴ and R²⁵ are taken together with the nitrogen atom towhich they are attached to form a 3- to 10-membered ring containing ringmembers selected from carbon atoms and up to 2 heteroatoms independentlyselected from one oxygen atom, one sulfur atom, and up to 2 nitrogenatoms, wherein up to 2 carbon atom ring members are independentlyselected from C(═O) and C(═S) and the sulfur atom ring member isselected from S, S(O) or S(O)₂, said ring being unsubstituted orsubstituted with up to 4 substituents independently selected from thegroup consisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; each Qis independently phenyl, a 5- or 6-membered heterocyclic aromatic ringor a 3- to 6-membered heterocyclic non-aromatic ring, each ringcontaining ring members selected from carbon atoms and up to 2heteroatoms independently selected from one oxygen atom, one sulfuratom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ringmembers are independently selected from C(═O) and C(═S) and the sulfuratom ring member is selected from S, S(O) or S(O)₂, each ringunsubstituted or substituted with at least one substituent independentlyselected from the group consisting of halogen, cyano, nitro, C₁-C₄alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄haloalkoxy; and each n is independently 0, 1 or
 2. 2. The compound ofclaim 1 wherein X¹ is CR¹ and X² is CH or N; or X¹ is CH or N, and X² isCR¹.
 3. The compound of claim 2 wherein X¹ is CR¹ and X² is CH; or X¹ isCH, and X² is CR¹.
 4. The compound of claim 3 wherein R¹ is a 5- or6-membered aromatic ring containing ring members selected from carbonatoms and up to 3 heteroatoms independently selected from one oxygenatom, one sulfur atom, and up to 3 nitrogen atoms, wherein up to 2carbon atom ring members are independently selected from C(═O) and C(═S)and the sulfur atom ring member is selected from S, S(O) or S(O)₂, eachring being substituted with one R³, and optionally further substitutedwith 1 to 3 R^(x).
 5. The compound of claim 4 wherein R¹ is phenyl,pyridinyl, thiazolyl, oxazolyl or oxadiazolyl, each being substitutedwith one R³, and optionally further substituted with 1 to 3 R^(x). 6.The compound of claim 5 wherein R³ is R^(3b) or R^(3e).
 7. A compositioncomprising a compound of claim 1 and at least one additional componentselected from the group consisting of surfactants, solid diluents andliquid diluents, said composition optionally further comprising at leastone additional biologically active compound or agent.
 8. The compositionof claim 7 wherein the at least one additional biologically activecompound or agent is selected from the group consisting of abamectin,acephate, acequinocyl, acetamiprid, acrinathrin, afidopyropen,amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl,benfuracarb, bensultap, bifenthrin, bifenazate, bistrifluron, borate,buprofezin, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole,chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl,chromafenozide, clofentezin, clothianidin, cyantraniliprole,cyclaniliprole, cycloprothrin, cycloxaprid, cyflumetofen, cyfluthrin,beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin,cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine,deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron,dimefluthrin, dimehypo, dimethoate, dinotefuran, diofenolan, emamectin,endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatinoxide, fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin,fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide,flucythrinate, flufenerim, flufenoxuron, flufenoxystrobin,flufensulfone, fluorpyram, flupiprole, flupyradifurone, fluvalinate,tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide,heptafluthrin, hexaflumuron, hexythiazox, hydramethylnon, imidacloprid,indoxacarb, insecticidal soaps, isofenphos, lufenuron, malathion,meperfluthrin, metaflumizone, metaldehyde, methamidophos, methidathion,methiodicarb, methomyl, methoprene, methoxychlor, metofluthrin,monocrotophos, monofluthrin, methoxyfenozide, nitenpyram, nithiazine,novaluron, noviflumuron, oxamyl, parathion, parathion-methyl,permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb,profenofos, profluthrin, propargite, protrifenbute, pyflubumide,pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl,pyrifluquinazon, pyriminostrobin, pyriprole, pyriproxyfen, rotenone,ryanodine, silafluofen, spinetoram, spinosad, spirodiclofen,spiromesifen, spirotetramat, sulprofos, sulfoxaflor, tebufenozide,tebufenpyrad, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos,tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam,thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate,trichlorfon, triflumuron, all strains of Bacillus thuringiensis,entomopathogenic bacteria, all strains of Nucleo polyhedrosis viruses,entomopathogenic viruses and entomopathogenic fungi.
 9. The compositionof claim 8 wherein the at least one additional biologically activecompound or agent is selected from the group consisting of abamectin,acetamiprid, acrinathrin, afidopyropen, amitraz, avermectin,azadirachtin, benfuracarb, bensultap, bifenthrin,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide,buprofezin, carbaryl, cartap, chlorantraniliprole, chlorfenapyr,chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole,cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin,lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran,diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox,etoxazole, fenitrothion, fenothiocarb, fenoxycarb, fenvalerate,fipronil, flometoquin, flonicamid, flubendiamide, flufenoxuron,flufenoxystrobin, flufensulfone, flupiprole, flupyradifurone,fluvalinate, formetanate, fosthiazate, heptafluthrin, hexaflumuron,hydramethylnon, imidacloprid, indoxacarb, lufenuron, meperfluthirn,metaflumizone, methiodicarb, methomyl, methoprene, methoxyfenozide,metofluthrin, monofluthrin, nitenpyram, nithiazine, novaluron, oxamyl,pyflubumide, pymetrozine, pyrethrin, pyridaben, pyridalyl,pyriminostrobin, pyriproxyfen, ryanodine, spinetoram, spinosad,spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide,tetramethrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium,tralomethrin, tetramethylfluthrin, triazamate, triflumuron, all strainsof Bacillus thuringiensis and all strains of Nucleo polyhedrosisviruses.
 10. A method for controlling an invertebrate pest comprisingcontacting the invertebrate pest or its environment with a biologicallyeffective amount of a compound of any one of claims 1-6.
 11. A treatedseed comprising a compound of any one of claims 1-6 in an amount of fromabout 0.0001 to 1% by weight of the seed before treatment.